JP2007039567A - Composite molded article for high-frequency electronic component and composition for producing composite molded article for high-frequency electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite molded article for a high-frequency electronic component, capable of reducing dielectric loss (or tanδ) in high-frequency band, especially GHz band; and to provide a method for producing the molded article, an electronic component, etc using the molded article. <P>SOLUTION: The composite molded article for the high-frequency electronic component contains 0.0001-0.1 wt.% at least one kind selected from the group consisting of a nanotube and a nanowire in the matrix. The method for producing the molded article, the resin composition for producing the molded article, the electronic component or the like formed by using the molded article or the resin composition are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composite molded body for high-frequency electronic components and a composition for producing a composite molded body for high-frequency electronic components. More specifically, the present invention relates to a resin molded body having a low dielectric loss tangent and suitable for manufacturing electronic parts. Moreover, this invention relates to the manufacturing method of this resin molding, the composition for manufacture of the composite molding for high frequency electronic components, an electronic component provided with this resin molding, and a printed wiring board.

  In recent years, with the rapid increase in the amount of communication information, there has been a strong demand for miniaturization, weight reduction, and speedup of information communication devices such as PHS and mobile phones, and a low dielectric electrical insulating material that can cope with this demand is demanded. . In particular, the frequency band of radio waves used in mobile communication devices such as portable mobile communications such as car phones and digital mobile phones, satellite communications, etc. is in the high frequency band of mega to giga Hz. In addition, since the usable wavelength band is decreasing, utilization of high frequency bands such as microwave and millimeter wave bands has been advanced. Further, the CPU clock time of the computer has reached the GHz band, and the frequency has been increased. In order to reduce the size and weight of a communication device corresponding to such a high frequency band, it is necessary to develop an electrically insulating material having both excellent high frequency transmission characteristics and low dielectric characteristics.

  Along with the downsizing and high performance of electronic devices, printed wiring boards mounted in them are becoming more dense due to higher layers, thinner materials, smaller through-hole diameters, and reduced hole spacing. .

  In addition, the printed wiring boards mounted on information terminal devices such as mobile phones and mobile computers can transfer high-capacity information at high speed, centering on plastic packages that mount MPUs directly on printed wiring boards and printed wiring boards for various modules. Therefore, high-speed signal processing, low transmission loss, and further downsizing are required.

  For this reason, printed wiring boards are becoming more dense and require finer wiring than ever before, and are required to be made of a material having excellent dielectric characteristics.

  A printed wiring board or module printed wiring board on which such an MPU is mounted is required to have a high Tg material having excellent heat resistance in order to ensure connection reliability higher than ever. Further, in order to cope with high-speed signal processing, a low dielectric constant / low dielectric loss tangent material is required.

  However, since the high Tg resin material has hard and brittle characteristics, it has a drawback of poor adhesion to the copper foil. In addition, the low dielectric constant / low dielectric loss tangent material has a drawback that it has poor adhesion to the copper foil in order to reduce the polar groups of the resin skeleton.

  With a resin material having low adhesiveness to the copper foil, line peeling or disconnection is likely to occur during substrate molding or mounting, and the adhesiveness with the copper foil becomes an important characteristic as fine wiring becomes more advanced in the future.

  Circuit board materials for electronic devices are often required to have low dielectric properties such as relative permittivity and dielectric loss tangent, and excellent physical properties such as heat resistance and mechanical strength. The relative dielectric constant (ε) is a parameter indicating the degree of polarization in the dielectric, and the higher the relative dielectric constant, the greater the propagation delay of the electrical signal. Therefore, in order to increase the signal propagation speed and enable high-speed calculation, it is preferable that the relative dielectric constant is low. The dielectric loss tangent (tan δ) is a parameter indicating the amount of the signal propagated through the dielectric that is lost by being converted into heat. The lower the dielectric loss tangent, the smaller the signal loss and the better the signal transmissibility.

  That is, an energy loss in the transmission process called dielectric loss occurs in the element circuit, but this energy loss is not preferable because it is released into the element circuit as thermal energy. This energy loss occurs because a dipole generated by dielectric polarization vibrates due to a change in electric field in the low frequency band, and occurs due to ion polarization or electronic polarization in the high frequency band. The ratio of the energy consumed in the dielectric per cycle of the alternating electric field to the energy stored in the dielectric is called the dielectric loss tangent and is expressed by tan δ.

  Since tanδ increases with increasing frequency in the high frequency band, and the amount of heat generated per unit area increases due to high-density mounting of electronic elements, in order to reduce the dielectric loss of the insulating material as much as possible, It is necessary to use a small material. By using a low dielectric polymer material with low dielectric loss, heat generation due to dielectric loss and electrical resistance is suppressed, resulting in fewer signal malfunctions. Therefore, transmission loss (energy loss) in the high-frequency communication field There is a strong demand for materials with a low content.

  As materials having electrical characteristics such as electrical insulation and low dielectric constant, thermoplastic resins such as polyolefin, vinyl chloride resin, fluorine resin, unsaturated polyester resin, polyimide resin, epoxy resin, bismaleimide are usually used. Various thermosetting resins such as triazine resin (BT resin), crosslinkable polyphenylene oxide, and curable polyphenylene ether have been developed to satisfy the following characteristics.

・ Drilling workability and cutting workability of laminates ・ High heat resistance ・ Low linear expansion coefficient ・ Adhesion or adhesion to metal conductor layer (copper foil adhesion)
・ Mechanical strength ・ Thin film forming ability ・ Relative permittivity can be set arbitrarily over a relatively wide range ・ Insulation ・ Weather resistance ・ Dielectric properties are less dependent on temperature and humidity.

  However, the resin has the following problems.

(1) Polyolefin Polyolefins such as polyethylene and polypropylene have a covalent bond such as a C—C bond and do not have a large polar group, so they have excellent electrical properties, particularly insulation resistance, but have low heat resistance. There is a drawback. For this reason, electrical characteristics (dielectric loss, relative dielectric constant, etc.) in use at high temperatures deteriorate, and it cannot be said that it is suitable as an insulating film (layer) such as a capacitor.

  Polyethylene and polypropylene are once formed as a film, and this is coated and bonded to a conductive material using an adhesive, but this method not only complicates the processing steps but also reduces the thickness of the film forming layer. There are also problems in forming the coating, such as very difficult.

(2) Vinyl chloride resin Although vinyl chloride resin has high insulation resistance and excellent chemical resistance and flame retardancy, it has the disadvantages of lacking heat resistance and large dielectric loss like polyolefin.

(3) Vinylidene fluoride resin, trifluoroethylene resin, and perfluoroethylene resin These polymers containing fluorine atoms in the molecular chain have electrical properties (low dielectric constant, low dielectric loss), heat resistance, chemical properties. Although it is excellent in stability, it has difficulty in forming process such as obtaining a molded product or a film by heat treatment like a thermoplastic resin, coating film forming ability, and when making a device, The cost is considerably high. Furthermore, there is a drawback that application fields are limited due to low transparency.

(4) Epoxy resin Conventionally, a system for curing an epoxy resin with dicyandiamide has been widely used for printed wiring boards. However, the dicyandiamide curing system has a drawback that the hygroscopicity is high, and it is difficult to satisfy high insulation reliability associated with further increase in the density of the printed wiring board in the future.

  On the other hand, in a system using a polyfunctional phenol resin as a curing agent, a printed wiring board having a low water absorption and a Tg of 170 ° C. or higher can be obtained.

  However, the printed wiring board using such polyfunctional phenol may cause a problem of discoloration during heat treatment depending on the type of phenol.

  Japanese Patent Publication No. 62-28168 proposes a system containing a high-orthophenol / formaldehyde resin mainly composed of phenol or bisphenol A for the purpose of improving the heat discoloration. The Tg resin material is hard and brittle, and the polyfunctional phenol-curing system has a low adhesiveness to the copper foil because the resin has a lower polarity than the dicyandiamide curing system.

  As a technique for improving the adhesion between the copper foil and the resin, a copper foil treatment with a coupling agent or the like as in JP-A-54-48879 has been performed for a long time. In the case of a brittle resin system, it is inferior to the adhesiveness of the conventional FR-4 material, and is not sufficient for strengthening the chemical bond with a resin to the extent that it is treated with a commercially available coupling agent.

  In addition, in the copper foil treatment with a silane coupling agent, a residue may remain on the substrate surface after circuit formation, which may adversely affect plating contamination and adhesion with a solder resist in the subsequent plating step.

(5) Polyimide, polyethersulfone, polyphenylene sulfide, polysulfone, thermosetting polyphenylene ether (PPE), polyethylene terephthalate Performance required for low dielectric constant materials with excellent dielectric properties and insulation resistance A soldering process is always required, so heat resistance is required to withstand at least heating at 260 ° C for 120 seconds, chemical stability such as heat resistance and alkali resistance, and excellent moisture resistance and mechanical properties. Must be a thing. As polymer materials that satisfy these requirements, for example, polyimide, polyethersulfone, polyphenylene sulfide, polysulfone, thermosetting polyphenylene ether (PPE), polyethylene terephthalate, and the like are known. However, even with these resins, dielectric loss increases in the GHz band.

  Thus, since the resin alone has various difficulties in achieving the above-described characteristics, it has been proposed to add an additive to the resin to improve the electrical properties of the resin. For example, when a specific amount of a specific metal silicate-based fibrous material is blended with a synthetic resin, thermal conductivity and heat resistance are not increased without causing an increase in relative permittivity and dielectric loss tangent that hinders use in a high frequency range. In addition, depending on the type of resin to be blended, the dielectric loss tangent can be significantly reduced while maintaining the same relative dielectric constant. It has been proposed that it can be used very suitably as a circuit board material, which is an electrical application different from the electric / electronic parts that have been used, particularly as a circuit board material for high frequency (Patent Document 1).

More specifically, in the Patent Document 1, (excluding the polyamide resin) thermoplastic resin and / or thermosetting resin (excluding phenol resins), the general formula _{aMx Oy · bSiO 2 · cH 2} O ( wherein a, b and c are positive real numbers, y is 1 when x is 1, and y is 1 or 3 when x is 2, M is Mg, Cr, Mn, Fe, Co, At least one metal element selected from the group consisting of Ni, Cu, Zn, Al, Ga, Sr, Y, Zr, Nb, Mo, Pb, Ba, W, and Li. A resin for high-frequency electronic parts, comprising reinforcing fibers mainly composed of a metal salt-based fibrous substance in a proportion of 5 to 60% by weight based on the total weight of the resin and the fibrous substance. A composition is proposed.

  However, in the said patent document 1, the compounding ratio of the reinforced fiber with respect to a thermoplastic resin or a thermosetting resin is at least about 5 weight% or more, and it is necessary to use this reinforced fiber in large quantities.

  Patent Document 2 describes a carbon nanotube composite molded body characterized in that carbon nanotubes are molded in a polymer matrix arranged in a certain direction and combined, and the molded body is described as follows. It describes that it exhibits anisotropic functions with respect to electrical properties, thermal properties, mechanical properties, and the like. The amount of carbon nanotubes to be blended in the polymer matrix is preferably in the range of 0.01 to 100 parts by weight per 100 parts by weight of the matrix. When the blending amount is less than 0.01 parts by weight, the anisotropic function is exhibited. It is described that it cannot be fully expressed.

Further, Patent Document 3 describes a nanocomposite dielectric including a polymer matrix and a plurality of carbon nanotubes dispersed in the polymer matrix, and the additive concentration near the percolation threshold of the carbon nanotubes in the matrix. Although it is disclosed that the presence of the conductive component increases the dielectric constant and at the same time increases the dielectric loss tangent, it does not specifically describe reducing the dielectric loss tangent.
JP-A-8-134263 JP 2002-273741 A (see claim, paragraph 0030) Japanese translation of PCT publication No. 2005-500648 (see claim)

  A main object of the present invention is to provide a molded body for a high frequency electronic component capable of reducing a dielectric loss (or tan δ) in a high frequency band, particularly a GHz band.

  Another object of the present invention is to provide a method for producing such a molded body for a high-frequency electronic component and an electronic component using the molded body.

  As a result of intensive investigations aimed at achieving the above object, the present inventors have obtained the following knowledge.

  (a) When nanotubes or nanowires are present in a matrix in a small amount within a specific range, an increase in dielectric loss tangent is suppressed in a high frequency band, particularly in the GHz band, as compared with a matrix alone.

  (b) an organic resin matrix and at least one selected from the group consisting of a plurality of nanotubes and nanowires present in an arrayed state in the organic resin matrix, and at least selected from the group consisting of the nanotubes and nanowires When one kind is present in a small amount within a specific range, an increase in dielectric loss tangent is suppressed in a high-frequency band, particularly in the GHz band, as compared with a matrix alone.

  (c) When the transition metal-containing nanoscale carbon tube is present in the matrix in a small amount within a specific range, an increase in dielectric loss tangent is suppressed in the high frequency band, particularly in the GHz band, as compared with the matrix alone.

  The present invention has been completed based on such findings, and has been completed. The present invention provides the following resin molded body for electronic parts, a manufacturing method thereof, electronic parts, and the like.

  [Item 1] The composite molding for high-frequency electronic components, wherein the matrix contains at least one member selected from the group consisting of nanotubes and nanowires in an amount of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix. body.

  [Item 2] The composite for a high-frequency electronic component according to Item 1, wherein the matrix is selected from the group consisting of a low-molecular organic matrix, an organic resin matrix, a low-molecular inorganic matrix, an inorganic resin matrix, and a composite thereof. Molded body.

  [Item 3] The composite molded body for a high-frequency electronic component according to Item 1, wherein the matrix is an organic resin matrix.

[Claim 4] The organic resin forming the organic resin matrix is
(i) a thermoplastic resin, or
(ii) thermosetting resin, or
(iii) radiation curable resin, or
(iv) a composite resin comprising two or more selected from the group consisting of thermoplastic resins, thermosetting resins and radiation curable resins, or
(v) The composite molded article for a high-frequency electronic component according to Item 3, which is a mixture of two or more of (i) to (iv) above.

  [Item 5] The composite molded body for high-frequency electronic components according to any one of Items 1 to 4, wherein the matrix has a relative dielectric constant at 1 GHz of less than 10.

  [Item 6] The composite molded body for a high-frequency electronic component according to any one of Items 1 to 4, wherein the matrix has a relative dielectric constant at 1 GHz of less than 5.

  [Item 7] The composite molded body for a high-frequency electronic component according to any one of Items 1 to 4, wherein the matrix has a dielectric loss tangent at 1 GHz of less than 0.5.

  [Item 8] The matrix is a low molecular organic matrix, an organic resin matrix, or a composite thereof, and is the lowest of the melting point, softening point, or glass transition point of the low molecular organic matrix, the organic resin matrix, or a composite thereof. Item 8. The composite molded article for a high-frequency electronic component according to any one of Items 1 to 7, wherein the low temperature is 60 ° C. or higher and lower than 500 ° C.

  [Item 9] The matrix is a low-molecular organic matrix, an organic resin matrix, or a composite thereof, and has a linear expansion coefficient at the lowest temperature or lower than the melting point, softening point, or glass transition point thereof. Item 8. The composite molded article for high-frequency electronic components according to any one of Items 1 to 7, which is 1 ppm or more and less than 1000 ppm.

  [Item 10] The composite molding for a high-frequency electronic component according to any one of Items 1 to 9, wherein at least one selected from the group consisting of the nanotube and the nanowire is formed of a conductive material. body.

  [Item 11] The composite molded article for a high-frequency electronic component according to any one of Items 1 to 9, wherein at least one selected from the group consisting of the nanotube and the nanowire is a carbon nanotube.

  [Item 12] At least one selected from the group consisting of the nanotube and the nanowire is a single-walled carbon nanotube, a multi-walled carbon nanotube, an amorphous nanoscale carbon tube, or a transition metal-containing nanoscale carbon tube, having a diameter of 1 to 100 nm, Item 10. The composite molded article for high-frequency electronic components according to any one of Items 1 to 9, having an aspect ratio of 10 to 5000.

  [Item 13] At least one selected from the group consisting of the nanotube and the nanowire is a transition metal-containing nanoscale carbon tube, and the content of the transition metal is equivalent to the weight of the transition metal nanoscale carbon tube in terms of transition metal carbide. Item 10. The composite molded article for high-frequency electronic components according to any one of Items 1 to 9, which is 0.1 wt% or more and less than 50 wt%.

  [Item 14] At least one selected from the group consisting of nanotubes and nanowires is a transition metal-containing nanoscale carbon tube, and the transition metal is at least one selected from the group consisting of iron, cobalt, and nickel. Item 10. The composite molded article for a high-frequency electronic component according to any one of Items 1 to 9, wherein

  [Item 15] At least one selected from the group consisting of the nanotubes and nanowires is a transition metal-containing nanoscale carbon tube, and the inner space of the tube is selected from the group consisting of iron, cobalt, nickel, and their carbides. At least one selected from the group consisting of iron, cobalt, nickel and their carbides is 1 weight of the weight of the transition metal-containing nanoscale carbon tube in terms of transition metal carbide Item 15. The composite molded article for high-frequency electronic components according to Item 14, which is at least%.

  [Item 16] An organic resin matrix 100 comprising at least one selected from the group consisting of nanotubes and nanowires and an organic resin matrix, wherein at least one selected from the group consisting of nanotubes and nanowires is in a partially connected state. A composite molded body for a high-frequency electronic component, which is present in a ratio of 0.0001 to 0.1 parts by weight with respect to parts by weight.

  CLAIM | ITEM 17 The composite molded object for high frequency electronic components of claim | item 16 whose nanotube or nanowire or these aggregate | assembly has the curvature of the range of 0.5-5.0 micrometers.

  [Item 18] The composite molded article for a high-frequency electronic component according to Item 16, wherein the free ion contained in the nanotube or nanowire is 200 ppm or less and the halogen content is 400 ppm or less.

  [Item 19] At least one selected from the group consisting of nanotubes and nanowires is blended with an organic resin in a solution state, a fluid state, or a molten state above the glass transition point or above the melting point, and then solvent removal and photocuring. A method for producing a composite molded body for a high-frequency electronic component, wherein the organic resin is solidified by reaction, thermosetting reaction, or cooling treatment.

  [Item 20] In the organic resin matrix, at least one selected from the group consisting of nanotubes and nanowires is previously mixed and dispersed at a concentration of 0.01 parts by weight to 50 parts by weight with respect to 100 parts by weight of the organic resin matrix. And manufacturing the resin composition obtained by dispersing the concentrated mixed dispersion in the organic resin matrix so that the carbon nanotubes or nanowires are 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the organic resin matrix, Item 20. The method for producing a composite molded body for a high-frequency electronic component according to Item 19, wherein the organic resin is solidified by solvent removal, photocuring reaction, thermosetting reaction, or cooling treatment.

  [Item 21] The high frequency electronic component according to item 19 or 20, wherein the nanotube is solidified and molded in a state where a part of the nanotubes or nanowires are connected to each other in an organic resin matrix under application of an electric field or a magnetic field. A method for producing a composite molded body.

  [Item 22] Forming by solidification in a coiled or arcuate state in which a part of nanotubes or nanowires are connected to each other under application of an electric or magnetic field and have a curvature range of 0.5 to 5.0 μm. Item 21. The method for producing a composite molded body for a high-frequency electronic component according to Item 19 or 20.

  [Item 23] The matrix is an organic resin matrix, and the organic resin matrix is (a) an epoxy resin, (b) an addition condensate of bisphenol A and formaldehyde, (c) a curing accelerator, and (d) a triazine ring or an isocyanuric ring. Item 5. The composite molded article for high-frequency electronic components according to Item 1, which contains a compound having a nitrogen content or a compound excluding a urea derivative and having a nitrogen content of 60% by weight or less as an essential component.

  [Item 24] (b) An addition condensate of bisphenol A and formaldehyde has a phenolic hydroxyl group in the range of 0.5 to 1.5 equivalents relative to the epoxy group of the epoxy resin, and (c) a curing accelerator is 100 weight of epoxy resin. 0.01 to 5 parts by weight and (d) a compound having a triazine ring or isocyanuric ring or a compound having a nitrogen content of 60% by weight or less not containing a urea derivative in a hot air drying oven at 210 ° C. for 30 minutes. Item 24. The composite molded article for high-frequency electronic components according to Item 23, wherein the nitrogen content is in a range of 0.1 to 10% by weight with respect to the resin solid content calculated from the weight ratio before and after the treatment.

  [Item 25] The composite molded article for a high-frequency electronic component according to Item 23 or 24, which contains (e) a flame retardant in addition to (a) to (d).

  [Item 26] The composite molded article for a high-frequency electronic component according to Item 25, wherein the retarding agent of (e) is tetrabromobisphenol A or glycidyl ether of tetrabromobisphenol A.

  [Item 27] The composite molded body for high-frequency electronic components, wherein the matrix contains at least one member selected from the group consisting of nanotubes and nanowires in an amount of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix. Composition.

  [Item 28] The composition for a composite molded article for a high-frequency electronic component according to Item 27, wherein the matrix is an organic resin matrix.

  [Item 29] The high-frequency electron according to item 28, wherein the composition containing nanotubes or nanowires in an organic resin matrix is a resin adhesive for electronic parts, a resin insulating film, a solder resist, or a semiconductor sealing resin. Composition for composite molded body for parts.

  CLAIM | ITEM 30 The composite molded object for high frequency electronic components formed from the composition for complex molded objects for high frequency electronic components in any one of claim | item 27-29.

  [Item 31] A resin-coated metal foil comprising a metal foil and a cured layer of the composition for a composite molded article for a high-frequency electronic component according to Item 29.

  [Item 32] A printed wiring board comprising a cured layer of the composite molded body composition for a high-frequency electronic component according to Item 29.

  CLAIM | ITEM 33 The electrical circuit formation method or printed wiring board preparation method characterized by using the resin composition for composite molded objects for high frequency electronic components of claim | item 27.

  [Item 34] An electronic component using the printed wiring board according to item 32 as a part of the component.

  [Item 35] An electrical device using the printed wiring board according to Item 32 as a part of a part.

  [Item 36] An insulating film formed by casting or braiding an organic resin matrix containing at least one selected from the group consisting of nanotubes and nanowires.

  [Item 37] A method for producing an insulating film, comprising casting or braiding an organic resin matrix containing at least one selected from the group consisting of nanotubes and nanowires.

  [Item 38] A substrate is impregnated with a composition containing at least one selected from the group consisting of nanotubes and nanowires in an amount of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix, impregnated into a substrate, and dried. A metal foil is laminated on one or both surfaces of at least one of the prepregs obtained in this manner, and heat-pressed to obtain a metal-clad laminate, and a circuit is formed in the metal-clad laminate. Printed wiring board.

  [Item 39] A composition containing at least one selected from the group consisting of nanotubes and nanowires in a matrix in an amount of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix is used as a varnish, and the varnish is formed on the film. A printed wiring board or a multilayer substrate obtained by using an insulating film obtained by coating and drying on a substrate.

  [Item 40] A resin adhesive for electronic parts, comprising at least one selected from the group consisting of nanotubes and nanowires in an organic resin matrix.

  [Item 41] A resin insulating film, a resin-coated metal foil, a solder resist, or a semiconductor sealing resin formed using the resin adhesive for electronic components according to Item 40.

  [Item 42] An electric circuit or printed wiring board using a resin insulating film, a metal foil with resin, a solder resist, and a semiconductor sealing resin formed using the resin adhesive for electronic components according to Item 40.

  CLAIM | ITEM 43 The electrical circuit formation method or printed wiring board preparation method using the resin adhesive for electronic components of claim | item 40.

  The molded product of the present invention has a low dielectric loss tangent. In particular, the nanotubes or nanowires used in the present invention have the effect of suppressing the increase in dielectric loss tangent on the high frequency side. Therefore, when a material having a low dielectric loss tangent is originally used as a matrix and mixed and dispersed in the matrix, higher frequency is achieved. Side performance can be improved. Further, the dielectric loss tangent of the resin matrix provided with functions such as photosensitivity and molding processing tends to increase. Since the nanotubes or nanowires used in the present invention have an effect of suppressing the increase in dielectric loss tangent on the high frequency side, the dielectric loss tangent in the high frequency region can be reduced by mixing and dispersing in a functional resin matrix.

  The present invention, as described above, includes a nanotube or nanowire in a matrix, and the nanotube or nanowire is present in a ratio of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix. A composite molded body for electronic parts is provided.

1. Nanotubes and Nanowires In the present invention, at least one selected from the group consisting of nanotubes and nanowires is dispersed in a matrix. At least one selected from the group consisting of nanotubes and nanowires is preferably formed of a conductive material.

(1) Nanotubes As the nanotubes used in the present invention, various types of nanotubes can be used. For example, a carbon tube having a nano-sized diameter can be exemplified. Examples of such nano-sized carbon tubes include single-walled carbon nanotubes, multi-walled carbon nanotubes, amorphous nanoscale carbon tubes, and transition metal-containing nanoscale carbon tubes. Details of these will be described later. These nanotubes can be used in a wide range of sizes. Particularly, the diameter is 1 to 100 nm, particularly 5 to 70 nm, the length is 0.1 to 50 μm, particularly 0.2 to 10 μm, An aspect ratio of 10 to 5000, particularly 20 to 2000 is preferred.

  The diameter is a value measured by transmission electron microscope observation, the length is a value measured by a laser microscope, and the aspect ratio is a diameter measured by the transmission electron microscope observation and laser microscope observation. Is calculated from the length measured by

  As said transition metal containing nanoscale carbon tube, what contains at least 1 sort (s) selected from the group which consists of iron, cobalt, and nickel or these carbides as a transition metal can be illustrated, for example. The transition metal content is, for example, 0.1% by weight or more and less than 50% by weight of the transition metal-containing nanoscale carbon tube in terms of transition metal carbide.

  Among these transition metal-containing nanoscale carbon tubes, those containing the above transition metal, in terms of transition metal carbide, 1% by weight or more of the transition metal-containing nanoscale carbon tube, particularly 3 to 20% by weight, preferable.

  Among these transition metal-containing nanoscale carbon tubes, (a) a carbon tube selected from the group consisting of nanoflake carbon tubes and nested multi-walled carbon nanotubes and (b) iron carbide or iron, the carbon tube ( The iron-carbon composite in which the iron carbide or iron of (b) is filled in the range of 10 to 90% of the space in the tube of a) is preferable.

  In addition, single-walled or multi-walled carbon nanotubes containing iron can be used.

A carbon nanotube is a hollow carbon material in which a graphite sheet (that is, a carbon atom plane or graphene sheet of a graphite structure) is closed in a tube shape, its diameter is nanometer scale, and the wall structure has a graphite structure. ing. Among the carbon nanotubes, one with a single graphite sheet whose wall structure is closed in a tube shape is called a single-walled carbon nanotube, and a plurality of graphite sheets are each closed in a tube shape and are nested. It is called a multi-walled carbon nanotube with a nested structure. In the present invention, both of these single-walled carbon nanotubes and nested multi-walled carbon nanotubes can be used.

  The single-walled carbon nanotube that can be used in the present invention preferably has a diameter of about 1 to 100 nm and a length of about 0.1 to 50 μm, and has a diameter of about 2 to 70 nm and a length of about 0.1 to 20 μm. Those having a diameter of about 3 to 20 nm and a length of about 0.2 to 10 μm are particularly preferable.

  The nested multi-walled carbon nanotubes that can be used in the present invention preferably have a diameter of about 10 to 200 nm and a length of about 0.1 to 50 μm, a diameter of about 20 to 100 nm, and a length of 0.2. Those having a diameter of about -5 μm are more preferred, and those having a diameter of about 20-70 nm and a length of about 0.2-10 μm are particularly preferred.

Amorphous nanoscale carbon tube The amorphous nanoscale carbon tube is described in WO00 / 40509 (Japanese Patent No. 3355442), has a main skeleton made of carbon, and has a diameter of 0.1 to 1000 nm. , A nanoscale carbon tube having an amorphous structure, having a linear shape, and a plane of a carbon network plane (002) measured by a diffractometer method in an X-ray diffraction method (incident X-ray: CuKα) The interval (d002) is 3.54 mm or more, particularly 3.7 mm or more, the diffraction angle (2θ) is 25.1 degrees or less, particularly 24.1 degrees or less, and the half width of the 2θ band is 3.2 degrees or more, In particular, it is characterized by being 7.0 degrees or more.

  The amorphous nanoscale carbon tube is a thermally decomposable resin having a decomposition temperature of 200 to 900 ° C. in the presence of a catalyst made of at least one metal chloride such as magnesium, iron, cobalt, nickel, etc. It can be obtained by subjecting tetrafluoroethylene, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol or the like to excitation treatment.

  The shape of the thermally decomposable resin as a starting material may be any shape such as a film shape, a sheet shape, a powder shape, or a lump shape. For example, when obtaining a carbon material in which a thin amorphous nanoscale carbon tube is formed on a substrate, excitation treatment may be performed under appropriate conditions with a thermally decomposable resin applied or placed on the substrate. .

  As the excitation treatment, for example, heating is performed in an inert atmosphere, preferably in a temperature range of about 450 to 1800 ° C. and at or above the thermal decomposition temperature of the raw material, and in a temperature range of about room temperature to 3000 ° C. Examples of the processing such as the above plasma processing can be given.

  The amorphous nanoscale carbon tube used in the present invention is a nanoscale carbon nanotube having an amorphous structure (amorphous structure), has a hollow linear shape, and the pores are highly controlled. The shape is mainly a cylinder, a quadrangular prism, etc., and at least one of the tips often has no cap (open). When the tip is closed, the shape is often flat.

  The outer diameter of the amorphous nanoscale carbon tube is usually in the range of about 1 to 1000 nm, preferably in the range of about 1 to 200 nm, and more preferably in the range of about 1 to 100 nm. The aspect ratio (tube length / diameter) is 2 times or more, preferably 5 times or more.

  Here, “amorphous structure” means a carbonaceous structure consisting of an irregular carbon network plane, not a graphite structure consisting of a continuous carbon layer of regularly arranged carbon atoms. The graphene sheets are irregularly arranged. From an image obtained by a transmission electron microscope, which is a typical analysis technique, the nanoscale carbon tube having an amorphous structure according to the present invention has a spread in the plane direction of the carbon network plane that is one time larger than the diameter of the amorphous nanoscale carbon tube. small. As described above, the amorphous nanoscale carbon tube has an amorphous structure in which a large number of fine graphene sheets (carbon network surface) are irregularly distributed instead of a graphite structure, so that the outermost layer is formed. The carbon mesh surface is not continuous over the entire length in the tube longitudinal direction but is discontinuous. In particular, the length of the carbon network surface constituting the outermost layer is less than 20 nm, particularly less than 5 nm.

Amorphous carbon generally does not exhibit X-ray diffraction, but exhibits broad reflection. In the graphitic structure, the carbon mesh planes are regularly stacked, so the carbon mesh plane spacing (d ₀₀₂ ) is narrowed, and the broad reflection shifts to the high angle side (2θ) and becomes gradually sharper (in the 2θ band). It becomes observable as d ₀₀₂ diffraction lines (d ₀₀₂ = 3.354 mm when they are regularly stacked due to the graphite positional relationship).

The theoretical crystallographic properties of the amorphous nanoscale carbon tube according to the present invention measured by the diffractometer method in the X-ray diffraction method (incident X-ray = CuKα) are defined as follows: carbon network plane The interval (d ₀₀₂ ) is 3.54 mm or more, more preferably 3.7 mm or more; the diffraction angle (2θ) is 25.1 degrees or less, more preferably 24.1 degrees or less; the half width of the 2θ band Is 3.2 degrees or more, more preferably 7.0 degrees or more.

Typically, the amorphous nanoscale carbon tube used in the present invention has a diffraction angle (2θ) by X-ray diffraction in the range of 18.9 to 22.6 degrees, and the carbon network plane spacing (d ₀₀₂ ) is 3.9 to 4.7 mm. The full width at half maximum of the 2θ band is in the range of 7.6 to 8.2 degrees.

  Of the transition metal-containing nanoscale carbon tubes, the iron-carbon composite will be described in detail as follows.

Iron-carbon composite The iron-carbon composite used in the present invention is described in Japanese Patent Application Laid-Open No. 2002-338220 (Japanese Patent No. 3569806), and (a) a nano-flake carbon tube and a multilayer of nested structure A carbon tube selected from the group consisting of carbon nanotubes and (b) iron carbide or iron, and the iron tube or iron of (b) is in a range of 10 to 90% of the space in the tube of the carbon tube (a). Filled. That is, 100% of the space in the tube is not completely filled, and the iron carbide or iron is filled in the range of 10 to 90% of the space in the tube (that is, partially). It is characterized in that it is filled in). The wall portion is a patchwork-like or machete-like (so-called paper mache-like) nano-flake carbon tube.

  In the claims and the specification of the present application, the “nano flake carbon tube” is composed of a plurality of (usually many) flake-like graphite sheets assembled into a patchwork shape or a paper mache shape. This refers to a carbon tube made of an aggregate of graphite sheets.

Such an iron-carbon composite is obtained according to the method described in JP-A-2002-338220.
(1) Ratio when the pressure is adjusted to 10 ⁻⁵ Pa to 200 kPa in an inert gas atmosphere, the oxygen concentration in the reactor is A (liter), and the oxygen amount is B (Ncc). Heating the iron halide to 600 to 900 ° C. in a reaction furnace adjusted to a concentration at which B / A is 1 × 10 ⁻¹⁰ to 1 × 10 ⁻¹ , and
(2) Manufactured by a production method including a step of introducing an inert gas into the reactor, introducing a pyrolytic carbon source at a pressure of 10 ⁻⁵ Pa to 200 kPa, and performing a heat treatment at 600 to 900 ° C. The

  Here, “Ncc”, which is a unit of the oxygen amount B, means a volume (cc) when converted to a standard state of gas at 25 ° C.

  The iron-carbon composite is composed of (a) a carbon tube selected from the group consisting of nano flake carbon tubes and nested multi-walled carbon nanotubes, and (b) iron carbide or iron, The space portion (that is, the space surrounded by the tube wall) is not substantially filled, but a part of the space portion, more specifically, about 10 to 90%, particularly about 30 to 80%. Preferably, about 40 to 70% is filled with iron carbide or iron.

  In the iron-carbon composite used in the present invention, as described in JP-A No. 2002-338220, the carbon portion is produced at a specific rate after performing the production steps (1) and (2). When cooled, it becomes a nano flake carbon tube, and after performing the manufacturing steps (1) and (2), heat treatment is performed in an inert gas, and cooling is performed at a specific cooling rate, thereby forming a multi-walled carbon nanotube with a nested structure. .

<(A-1) Nano flake carbon tube>
The nano-flake carbon tube of the present invention and the iron-carbon composite composed of iron carbide or iron are typically cylindrical, but such a cylindrical iron-carbon composite (Japanese Patent Laid-Open No. 2002-338220). A transmission electron microscope (TEM) photograph of a cross section substantially perpendicular to the longitudinal direction of the product obtained in Example 1 of FIG. 3 is shown in FIG. 3, and a side TEM photograph is shown in FIG.

  FIG. 4 (a-1) shows a schematic diagram of a TEM image of such a columnar nanoflake carbon tube. In (a-1) of FIG. 4, 100 schematically shows a TEM image in the longitudinal direction of the nano flake carbon tube, and 200 indicates a TEM image in a cross section substantially perpendicular to the longitudinal direction of the nano flake carbon tube. This is shown schematically.

  The nanoflake carbon tube constituting the iron-carbon composite used in the present invention typically has a hollow cylindrical shape, and when the cross section is observed by TEM, arc-shaped graphene sheet images are concentrically assembled. Each graphene sheet image forms a discontinuous ring, and when the longitudinal direction is observed with TEM, the substantially straight graphene sheet images are arranged in multiple layers almost parallel to the longitudinal direction. The individual graphene sheet images are not continuous over the entire length in the longitudinal direction, but are discontinuous.

  More specifically, the nanoflake carbon tube constituting the iron-carbon composite used in the present invention is perpendicular to the longitudinal direction, as is apparent from 200 in FIGS. 3 and 4 (a-1). When the cross section is observed by TEM, many arc-shaped graphene sheet images are concentrically (multi-layered tube shape), but each graphene sheet image is completely closed as shown in 210 and 214, for example. It does not form a continuous ring, but forms a discontinuous ring that is interrupted. Some graphene sheet images may be branched as indicated by 211. At the discontinuity point, a plurality of arc-shaped TEM images constituting one discontinuous ring may have a partially disturbed layer structure as indicated by 222 in FIG. As shown by 223, there may be a space between adjacent graphene sheet images, but a large number of arc-shaped graphene sheet images observed by TEM form a multilayer tube structure as a whole. Yes.

  Further, as is clear from 100 of FIGS. 1 and 4 (a-1), when the longitudinal direction of the nanoflake carbon tube is observed by TEM, a large number of substantially straight graphene sheet images are used in the present invention. Although it is arranged in multiple layers substantially parallel to the longitudinal direction of the iron-carbon composite, the individual graphene sheet images 110 are not continuous over the entire length in the longitudinal direction of the iron-carbon composite, and are discontinuous in the middle. It has become. Some graphene sheet images may be branched as indicated by reference numeral 111 in FIG. Further, at the discontinuous points, among the TEM images arranged in a layered manner, the TEM image of one discontinuous layer is at least partly adjacent to the adjacent graphene sheet image as indicated by 112 in FIG. In some cases, they may overlap each other, or as shown at 113, they may be slightly apart from the adjacent graphene sheet images, but a large number of substantially linear TEM images form a multilayer structure as a whole.

  The structure of the nanoflake carbon tube of the present invention is greatly different from the conventional multi-walled carbon nanotube. That is, as shown by 400 in FIG. 4A-2, the multi-walled carbon nanotube with a nested structure has a cross-sectional TEM image perpendicular to its longitudinal direction. As shown by 300 in FIG. 4 (a-2), the straight graphene sheet images 310 and the like continuous over the entire length in the longitudinal direction are arranged in parallel. Structure (concentric cylindrical or nested structure).

  Although the details have not been fully elucidated yet, the nano-flake carbon tube constituting the iron-carbon composite used in the present invention has a large number of flake-like graphene sheets overlapped in a patchwork or tension form. It seems to form a tube as a whole.

  Such a nano-flake carbon tube of the present invention and an iron-carbon composite made of iron carbide or iron encapsulated in the inner space of the tube are nested multi-walled carbon nanotubes as described in Japanese Patent No. 2546114. The structure of the carbon tube is greatly different from that of the composite in which the metal is included in the inner space of the tube.

  In the case of TEM observation of the nano-flake carbon tube constituting the iron-carbon composite used in the present invention, each graphene sheet image relates to a number of substantially linear graphene sheet images oriented in the longitudinal direction. The length is usually about 2 to 500 nm, particularly about 10 to 100 nm. That is, as indicated by 100 in FIG. 4 (a-1), a large number of TEM images of the substantially linear graphene sheet indicated by 110 are collected to constitute a TEM image of the wall portion of the nanoflake carbon tube. The length of each substantially linear graphene sheet image is usually about 2 to 500 nm, particularly about 10 to 100 nm.

  Thus, in the iron-carbon composite, the outermost layer of the nanoflake carbon tube constituting the wall portion is formed of a discontinuous graphene sheet that is not continuous over the entire length in the tube longitudinal direction. The length of the outer carbon net surface is usually about 2 to 500 nm, particularly about 10 to 100 nm.

  As described above, the carbon portion of the wall portion of the nano-flake carbon tube constituting the iron-carbon composite used in the present invention has a tube shape in which a large number of flake-like graphene sheets are oriented in the longitudinal direction. However, when measured by the X-ray diffraction method, the average distance (d002) between the carbon network surfaces has a graphite structure of 0.34 nm or less.

  Moreover, the thickness of the wall part which consists of a nano flake carbon tube of the iron-carbon composite used by this invention is 49 nm or less, Especially about 0.1-20 nm, Preferably it is about 1-10 nm, Comprising: Over the full length, And substantially uniform.

<(A-2) Nested multi-walled carbon nanotubes>
As described above, by performing the specific heating step after performing the steps (1) and (2), the carbon tube constituting the obtained iron-carbon composite becomes a multi-walled carbon nanotube having a nested structure.

  The nested multi-walled carbon nanotube thus obtained is a concentric tube in which a TEM image of a cross section perpendicular to the longitudinal direction forms a substantially perfect circle as indicated by reference numeral 400 in FIG. In addition, the graphene sheet images that are continuous over the entire length in the longitudinal direction are arranged in parallel (a concentric cylindrical or nested structure).

  The carbon portion of the wall portion of the multi-walled carbon nanotube of the nested structure constituting the iron-carbon composite used in the present invention has an average distance (d002) between carbon network surfaces of 0, as measured by X-ray diffraction. It has a graphite structure of 34 nm or less.

  Further, the thickness of the wall portion composed of the multi-walled carbon nanotube of the iron-carbon composite nested structure used in the present invention is 49 nm or less, particularly about 0.1 to 20 nm, preferably about 1 to 10 nm. Substantially uniform.

<(B) Iron carbide or iron contained>
In the present specification, the filling rate (10 to 90%) of the space inside the carbon tube selected from the group consisting of the nano flake carbon tube and the multi-walled carbon nanotube of the nested structure with iron carbide or iron is the iron used in the present invention. -Observing the carbon composite with a transmission electron microscope, and comparing the area of the image of the space of each carbon tube (ie, the space surrounded by the tube wall of the carbon tube) with the portion filled with iron carbide or iron. It is the ratio of the area of the image.

  The filling form of iron carbide or iron includes a form in which the space in the carbon tube is continuously filled and a form in which the space in the carbon tube is filled intermittently. Filled. Therefore, the iron-carbon composite used in the present invention should also be referred to as a metal-encapsulated carbon composite, an iron compound-encapsulated carbon composite, iron carbide, or an iron-encapsulated carbon composite.

  In addition, the iron carbide or iron included in the iron-carbon composite used in the present invention is oriented in the longitudinal direction of the carbon tube, has high crystallinity, and is in a range where iron carbide or iron is filled. The ratio of the area of the crystalline iron carbide or iron TEM image to the area of the TEM image (hereinafter referred to as “crystallization rate”) is generally about 90 to 100%, particularly about 95 to 100%.

  The high crystallinity of the iron carbide or iron contained is apparent from the fact that the TEM images of the inclusions are arranged in a lattice form when observed from the side of the iron-carbon composite of the present invention, It is clear from the fact that a clear diffraction pattern can be obtained in electron beam diffraction.

  Moreover, it can be easily confirmed by an electron microscope and EDX (energy dispersive X-ray detector) that iron carbide or iron is included in the iron-carbon composite used in the present invention.

<Overall shape of iron-carbon composite>
The iron-carbon composite used in the present invention is less curved, straight, and has a uniform thickness over the entire length of the wall, so it is homogeneous over the entire length. It has a shape. The shape is columnar and mainly cylindrical.

  The outer diameter of the iron-carbon composite according to the present invention is usually about 1 to 100 nm, particularly about 1 to 50 nm, preferably about 1 to 30 nm, more preferably about 10 to 30 nm. It is in. The aspect ratio (L / D) of the tube length (L) to the outer diameter (D) is about 5 to 10,000, and particularly about 10 to 1,000.

  The term “linear”, which is one term representing the shape of the iron-carbon composite used in the present invention, is defined as follows. That is, when the carbonaceous material containing the iron-carbon composite used in the present invention is observed in a range of 200 to 2000 nm square by a transmission electron microscope, the length of the image is W, and the image is linearly extended. In this case, the shape characteristic means that the ratio W / Wo is 0.8 or more, particularly 0.9 or more.

  The iron-carbon composite used in the present invention has the following properties when viewed as a bulk material. That is, in the present invention, iron- or iron carbide is filled in a range of 10 to 90% of the space in the tube of the carbon tube selected from the nano flake carbon tube and the nested multi-walled carbon nanotube as described above. The carbon composite is not a minute amount that can be barely observed by microscopic observation, but is a bulk material containing a large number of the iron-carbon composite, and is a carbonaceous material containing iron-carbon composite, or iron carbide or iron. It can be obtained in large quantities in the form of a material that should be referred to as an encapsulated carbonaceous material.

  FIG. 2 shows an electron micrograph of the carbonaceous material of the present invention comprising the nanoflake carbon tube produced in Example 1 of JP-A-2002-338220 and iron carbide filled in the space in the tube.

  As can be seen from FIG. 2, in the carbonaceous material containing the iron-carbon composite used in the present invention, basically, in almost all (particularly 99% or more) carbon tubes, the space (ie, In general, iron carbide or iron is filled in a range of 10 to 90% of the space surrounded by the tube wall of the carbon tube, and there is usually substantially no carbon tube in which the space portion is not filled. However, in some cases, a small amount of carbon tubes not filled with iron carbide or iron may be mixed.

  Further, in the carbonaceous material of the present invention, an iron-carbon composite in which 10 to 90% of the space portion in the carbon tube as described above is filled with iron or iron carbide is a main constituent component. In addition to the iron-carbonaceous composite, soot may be contained. In such a case, components other than the iron-carbonaceous composite of the present invention are removed to improve the purity of the iron-carbonaceous composite in the carbonaceous material of the present invention, which is substantially used in the present invention. A carbonaceous material consisting only of an iron-carbon composite can also be obtained.

  In addition, unlike materials that could only be confirmed in microscopic amounts by conventional microscopic observation, the carbonaceous material containing the iron-carbon composite used in the present invention can be synthesized in large quantities, and its weight can easily be increased to 1 mg or more. can do.

The carbonaceous material of the present invention is attributed to iron or iron carbide contained in powder X-ray diffraction measurement in which X-rays of CuKα are irradiated with an irradiation area of 25 mm ² or more with respect to 1 mg of the carbonaceous material. The integrated intensity of the peak showing the strongest integrated intensity among the peaks of ° <2θ <50 ° is Ia, and 26 ° <2θ <27 ° attributed to the average distance (d002) between the carbon network surfaces of the carbon tubes. When the integrated intensity Ib of the peak is set, the ratio R (= Ia / Ib) of Ia to Ib is preferably about 0.35 to 5, particularly about 0.5 to 4, more preferably 1 to 3. Degree.

In this specification, the ratio of Ia / Ib is referred to as an R value. This R value peaks as an average value of the entire carbonaceous material when the carbonaceous material containing the iron-carbon composite used in the present invention is observed in an X-ray diffraction method with an X-ray irradiation area of 25 mm ² or more. Since the strength is observed, not the inclusion rate or filling rate in one iron-carbon composite that can be measured by TEM analysis, but the entire carbonaceous material as an aggregate of iron-carbon composites, It shows the average value of iron filling rate or inclusion rate.

  In addition, the average filling rate as a whole carbonaceous material containing a large number of the present invention iron-carbon composites is observed by TEM, and a plurality of iron carbides in a plurality of iron-carbon composites observed in each field of view. It can also be obtained by measuring the average filling rate of iron and calculating the average value of the average filling rates of a plurality of visual fields. When measured by such a method, the average filling rate of iron carbide or iron as a whole carbonaceous material comprising the iron-carbon composite used in the present invention is about 10 to 90%, particularly about 40 to 70%.

  Among the iron-carbon composites that can be used in the present invention, for example, those with the following specifications are commercially available and are easily available.

Diameter: 20-40 nm,
Length: several μm to several tens of μm
Purity:> 90% (Purity is the probability that an iron-carbon complex exists for 100 fields of view by SEM observation at 5,000 times magnification)
Composition: C = 85 to 95 wt%, H> 0.1 wt%, N> 0.01 wt%, Fe = 5 to 15 wt%
Bulk density: O.1 ~ 0.2 g / cm ³
XRD:
・ Identification of crystal peaks: graphite, Fe ₃ C
-Crystallinity of graphite: half width of (002) peak = 0.9
・ Fe ₃ C / graphite ratio = Fe ₃ C (102) / C (002) = 0.05 ~ 2.0
(2) The nanowires used in the nanowire present invention, various materials can be used, preferably has a conductivity, e.g., Au, Ag, Sn, SiC , TiO, VO 2, WO 2, RuO 2, ReO Examples thereof include nanowires composed of ₂ , CrO ₂ , MoO ₂ , Fe ₃ O _{4 and the} like.

  These nanowires are known per se or can be produced according to known methods such as the CVD method.

  Various types of these nanowires can be used. Among them, the length is 0.1 to 50 μm, particularly 0.2 to 10 μm, the diameter is 1 to 100 nm, particularly 5 to 70 nm, and the aspect ratio is 10 Those having ˜5000, particularly 20˜2000 are preferred.

  In the present invention, the nanotube (1) and the nanowire (2) may be used in combination. Among the nanotubes of the above (1) and the nanowires of the above (2), free ions, for example, transition metal ions, alkali metal ions, etc. contained in the nanotubes or nanowires are 200 ppm or less, particularly 150 ppm or less, and the halogen content Is preferably 400 ppm or less, particularly 300 ppm or less. Such a nanotube or nanowire can be obtained by an arc discharge method, a laser ablation method, or a CVD method. If the above free ions and halogens are contained in the printed circuit board in an amount of 100 ppm or more, it causes a failure due to ion migration. Therefore, it is preferable that free ions are 200 ppm or less and halogen is 400 ppm or less.

2. Matrix In the present invention, a matrix is a binding material for dispersing nanotubes or nanowires to form a molded body. Specifically, any electrically insulating organic or inorganic material that does not have the shape of a nanotube or nanowire and is solid at room temperature is included.

  As the matrix, various types can be used, and examples thereof include a low molecular organic matrix, an organic resin matrix, a low molecular inorganic matrix, an inorganic resin matrix, or a matrix made of a composite thereof.

  The material constituting the low-molecular organic matrix may be any material that can be formed into a glass state by mixing a crystalline low-molecular compound or a material that can form a matrix with low molecules. For example, phthalocyanine or Benzocyclobutene and the like are known. Further, there can be exemplified substances as disclosed in JP-A-8-321217, 11-116663 and the like.

  Examples of the material constituting the organic resin matrix include various organic resins used in this field.

  Examples of the material constituting the inorganic resin matrix include siloxane-based materials such as hydrogenated silsesquioxane, methylsilsesquioxane, and hydrogenated methylsilsesquioxane.

  You may use the matrix which used those materials which comprise the said various matrix, and used those composites.

  Further, as a material constituting the matrix, for example, an inorganic compound (for example, polysiloxane, fluorinated silicon oxide, phosphazene, etc.), an organic-inorganic composite film (for example, silicone, trifluoromethylsilane, trimethoxyphenylsilane, triethoxy) Examples include organic silica films made of methylsilane, organic matrix filled with inorganic compounds, organic-inorganic hybrid films, etc., and phthalocyanine, benzocyclobutene, etc. as described above as the matrix other than the resin. It is also possible.

  Among these, a matrix made of an organic resin is preferable. A wide range of organic resins can be used as the matrix, such as (i) thermoplastic resins, (ii) thermosetting resins, (iii) radiation curable resins, and (iv) A composite resin composed of two or more of thermoplastic resins, thermosetting resins, and radiation curable resins, or (v) a mixture of two or more of (i) to (iv) above can be used. Examples of these matrices are “New materials and process technologies for next-generation ULSI multilayer wiring” (Technical Information Society of 2000), “Transforming packaging materials and layering technologies-high frequency, high density, low temperature sintering, environmental response- (2003 TIC). Among these, at least one resin selected from the group consisting of a thermoplastic resin, a thermosetting resin, and a composite resin of a thermoplastic resin and a thermosetting resin can be preferably used.

<Thermoplastic resin>
Examples of the thermoplastic resin include polyolefin resins such as polyethylene resin, polypropylene resin, poly 1-butene resin, poly 4-methyl-1-pentene resin; polyester resins such as polyethylene terephthalate resin and polyethylene naphthalate resin; nylon 6, nylon Polyamide resin such as 66; Fluorine resin such as polytetrafluoroethylene resin and polytrifluoride ethylene resin; Other polystyrene resin, polyvinyl chloride resin, polymethyl (meth) acrylate resin, polycarbonate resin, polyether sulfone resin, polyphenylene ether Examples thereof include resins and polyamideimide resins.

<Radiation curable resin>
As the radiation curable resin, those used in the field of electronic parts and the like can be widely used. Basically, it is possible to use a compound having two or more double bonds. In order to form a fine pattern, a side chain having a double bond and a carboxyl group for enabling aqueous development can be used. It is often used as an ultraviolet curable type. As these radiation curable resins, for example, those described in JP-A-61-243869, JP-A-2002-294131, JP-A-2005-154780 and the like can be used.

  Typically, examples of the radiation curable resin include those obtained by reacting “an ethylenically unsaturated monomer having a carboxyl group” with “a compound containing two or more epoxy groups”.

  Here, “compounds containing two or more epoxy groups” include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A-novolac type epoxy resin, alicyclic epoxy. Resin (for example, “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.) and a polyfunctional epoxy resin (for example, EPPN-502H manufactured by Nippon Kayaku Co., Ltd.) and Taku manufactured by Dow Chemical Co., Ltd. There are epoxy resins such as Tex-742 and XD-9053).

  In addition, as the “compound containing two or more epoxy groups”, the following copolymer of an epoxy compound and an ethylenically unsaturated monomer can also be used. That is, as epoxy compounds, glycidyl (meth) acrylates such as glycidyl (meth) acrylate and 2-methylglycidyl (meth) acrylate, and (meth) acrylic such as (3,4-epoxycyclohexyl) methyl (meth) acrylate And epoxycyclohexyl derivatives of acids. Examples of the ethylenically unsaturated monomer include aliphatic or alicyclic alkyl (meth) acrylates; aromatic (meth) acrylates such as benzyl (meth) acrylate; hydroxyethyl (meth) acrylate and methoxy Ethylene glycol ester (meth) acrylate such as ethyl (meth) acrylate, polyethylene glycol ester (meth) acrylate and propylene glycol (meth) acrylate; (meth) acrylamide compound; N-substituted maleimide compound; vinyl pyrrolidone; (Meth) acrylonitrile; vinyl acetate; styrene; α-methylstyrene; and vinyl ether.

  In this specification, (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid, and (meth) acrylate is a generic term for acrylate and methacrylate.

  Examples of the “ethylenically unsaturated monomer having a carboxyl group” include (meth) acrylic acid, crotonic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, 2-propenoic acid, 3- (2-carboxyethoxy) -3-oxypropyl ester, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid and 2- (meth) ) Those having one ethylenically unsaturated group such as acryloyloxyethyl hexahydrophthalic acid, and hydroxy such as pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. It includes those having a plurality of ethylenically unsaturated groups such as those obtained by reacting a dibasic acid anhydride to a polyfunctional acrylate having Le group. Among these, those having one carboxyl group are preferable, and it is particularly preferable to use (meth) acrylic acid or (meth) acrylic acid as a main component. This is because the ethylenically unsaturated group introduced by (meth) acrylic acid is excellent in photoreactivity. These “ethylenically unsaturated monomers having a carboxyl group” can be used alone or in appropriate combination.

  Moreover, as what added the carboxyl group for performing a double bond and aqueous development to a side chain, said "compound containing two or more epoxy groups" to "the ethylenically unsaturated monomer which has a carboxyl group" In addition, a product obtained by reacting the following “polycarboxylic carboxylic acid anhydride” can be raised. Examples of the “polycarboxylic anhydride” include succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Dibasic acid anhydrides such as methyl nadic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, and trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride and methylcyclohexene tetracarboxylic acid anhydride An acid anhydride having 3 or more basic acids may be mentioned. Each of these “polycarboxylic anhydrides” can be used alone or in appropriate combination.

<Thermosetting resin>
Examples of the thermosetting resin include polyimide resin, bismaleimide triazine resin (BT resin), crosslinkable polyphenylene oxide, curable polyphenylene ether, phenol resin, melamine resin, urea resin, epoxy resin, unsaturated polyester resin, alkyd resin, Diallyl phthalate resin, xylene resin, (meth) acrylic resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, bisphenol A, resorcin, various novolac type epoxy resins, bisphenol A type epoxy resin Examples include brominated bisphenol A type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, halogenated epoxy resins, and spirocyclic epoxy resins. .

<Composite resin>
Examples of the composite resin of the thermoplastic resin and the thermosetting resin include polyphenylene ether / epoxy resin, polyamideimide / epoxy resin, polyamide / epoxy resin, and polyamideimide / polyimide resin.

  Furthermore, in the present invention, as a matrix preferable for high-frequency applications, resins described in “Technological Trends of Low Resistive Polymers for Electronics” (Toray Research Center, 1999) are preferable. Resin, polyester resin, polycarbonate, polyimide, polyetherimide, polyphenylene sulfide, COPNA, polybenzimidazole, fluorine resin, fluorinated polymer, amorphous polyolefin resin, syndiotactic polystyrene, polynaphthalene, polyindane, polyphenylene ether, liquid crystal polymer , Polyquinoline, polyphenylquinoxaline, cyanate resin, polysulfone, polyethersulfone, polyetheretherketone, polyetherethernitrile, aromatic polyether, etc. Resins.

  Among them, the organic resin matrix contains (a) an epoxy resin, (b) an addition condensate of bisphenol A and formaldehyde, (c) a curing accelerator and (d) a compound having a triazine ring or an isocyanuric ring, or a urea derivative. It is preferable to contain a compound having no nitrogen content of 60% by weight or less as an essential component.

  Further, (b) the addition condensate of bisphenol A and formaldehyde is in the range of 0.5 to 1.5 equivalents of phenolic hydroxyl group to the epoxy group of the epoxy resin, and (c) the curing accelerator is 100 parts by weight of the epoxy resin. On the other hand, a compound having 0.01 to 5 parts by weight and (d) a compound having a triazine ring or an isocyanuric ring, or a compound having a nitrogen content of 60% by weight or less not containing a urea derivative has a nitrogen content of 0. It is preferable to contain so that it may become the range of 1-10 weight%.

  If necessary, in addition to the above (a) to (d), (e) a flame retardant can also be contained.

  Examples of the epoxy resin (a) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and bisphenol A novolak. Type epoxy resin, bisphenol F novolak type epoxy resin, phenol salicylaldehyde novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, other glycidyl etherified products of bifunctional phenols, two A glycidyl etherified product of a functional alcohol, a glycidyl etherified product of a polyphenol, a hydrogenated product thereof, a halide, etc. may be mentioned without particular limitation. Several kinds of these compounds can be used in combination.

  The addition condensate of bisphenol A and formaldehyde (b) functions as a curing agent for the epoxy resin (a), and there is no restriction on the molecular weight, and a bisphenol A monomer is contained. Also good.

  Further, as the component (b), a curing agent other than an addition condensate of bisphenol A and formaldehyde may be used in combination. For example, bisphenol F, polyvinylphenol or phenol, cresol, alkylphenol, catechol, bisphenol F and the like are used as raw materials. And novolak resin. There is no restriction | limiting also about the molecular weight of these compounds, Several types can be used together.

  (B) It is preferable that the compounding quantity of a component is the range whose phenolic hydroxyl group is 0.5-1.5 equivalent with respect to the epoxy group of an epoxy resin. Outside this range, the dielectric properties and heat resistance become poor.

  The curing accelerator (c) may be any compound as long as it has a catalytic function that promotes the etherification reaction of an epoxy group and a phenolic hydroxyl group. For example, an alkali metal compound, alkaline earth Examples thereof include metal compounds, imidazole compounds, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. Among them, it is preferable to use an imidazole whose imino group is masked with acrylonitrile, isocyanate, melamine acrylate, or the like, because a prepreg having storage stability twice or more that of the prior art can be obtained.

  Examples of the imidazole compound used here include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, and 2-heptadecylimidazole. 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole , 2-ethyl imidazoline, 2-isopropyl imidazoline, 2,4-dimethyl imidazoline, 2-phenyl-4-methyl imidazoline, etc., and the masking agents include acrylonitrile, phenylene diisocyanate. Sulfonates, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, isophorone diisocyanate, and the like melamine acrylate.

  Several kinds of these curing accelerators may be used in combination, and the blending amount is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin. When it is less than 0.01 part by weight, the promoting effect is small, and when it exceeds 5 parts by weight, the storage stability is deteriorated.

  Examples of the compound having a triazine ring or isocyanuric ring (d) or a compound having a nitrogen content of 60% by weight or less that does not contain a urea derivative include aromatic amine type epoxy resins, aliphatic amine type epoxy resins, and hydantoin types. There are epoxy resins, glycidylamine type epoxy resins, isocyanurate type epoxy resins, cyanurates, isocyanurates, melamines, addition condensates of phenols and compounds having a triazine ring and aldehydes, and glycidyl ethers thereof. There is no particular limitation. Any of these compounds may be used, and several types may be used in combination. These compounds are preferably blended so that the nitrogen content is 0.1 to 10% by weight with respect to the total resin solids used in the nanotube composite molded body or nanowire composite molded body for printed wiring boards. When the nitrogen content is less than 0.1% by weight, it is difficult to improve the adhesiveness with the copper foil, and when it exceeds 10% by weight, the water absorption is increased. Here, the total resin solid content is a resin solid content calculated from a weight ratio before and after the treatment for 30 minutes in a 210 ° C. hot air drying furnace.

  The flame retardant of the above (f) may be any as long as it is generally called a flame retardant, for example, bisphenol A, bisphenol F, bisphenol S, polyvinylphenol, phenol, cresol, alkylphenol, catechol. Although there are halides such as novolak resin, glycidyl ether, etc., there is no particular limitation, and antimony trioxide, tetraphenylphosphine, etc. may be used in combination. Among them, examples of the difficult agent include tetrabromobisphenol A or glycidyl ether of tetrabromobisphenol A.

  In the present invention, (a) an epoxy resin, (b) an addition condensate of bisphenol A and formaldehyde, (c) a curing accelerator and (d) a compound having a triazine ring or an isocyanuric ring, or a nitrogen content not containing a urea derivative By using a compound of 60% by weight or less, a nanotube composite molded body or a nanowire composite molded article for printed wiring boards having low hygroscopicity, excellent heat resistance and heat discoloration, and good adhesion to copper foil A body and a printed wiring board using the body can be obtained.

  That is, a printed wiring board using a nanotube composite molded body or a nanowire composite molded body for high-frequency electronic components according to an embodiment of the present invention includes (a) an epoxy resin, (b) an addition condensate of bisphenol A and formaldehyde, c) a accelerator and (d) a compound having a triazine ring or isocyanuric ring, or a compound containing no urea derivative and having a nitrogen content of 60% by weight or less, and (e) a nanotube composite molded body for a printed wiring board comprising nanotubes or nanowires Or it is a nanowire composite molded object.

  In the present invention, (b) the addition condensate of bisphenol A and formaldehyde has a phenolic hydroxyl group in the range of 0.5 to 1.5 equivalents relative to the epoxy group of the epoxy resin, and (c) the curing accelerator is an epoxy resin. A compound having a nitrogen content of 60% by weight or less containing 0.01 to 5 parts by weight with respect to 100 parts by weight and (d) a compound having a triazine ring or an isocyanuric ring or a urea derivative and containing no urea derivative has a nitrogen content of resin solids. , A nanotube composite molded body for a printed wiring board or a nanowire composite molded body that is contained in a range of 0.1 to 10% by weight.

  Furthermore, one embodiment of the present invention is a nanotube composite molded body or a nanowire composite molded body for a printed wiring board containing (f) a flame retardant in addition to the above (a) to (e), A nanotube composite molded body or a nanowire composite molded body for a printed wiring board, in which the difficult agent is tetrabromobisphenol A or glycidyl ether of tetrabromobisphenol A.

  Further, the present invention uses at least one or more prepregs obtained by impregnating and drying a substrate with a resin composition for producing the above-mentioned nanotube composite molded body for printed wiring boards or nanowire composite molded bodies. It is a printed wiring board obtained by laminating a metal foil on one side or both sides and heating and pressing.

  Furthermore, it is a nanotube composite molded body for printed wiring boards or a nanowire composite molded body that can be cured by radiation such as ultraviolet rays, visible light, X-rays, electron beams, and infrared rays.

  The radiation used in the radiation resin composition of the present invention uses infrared rays, visible rays, ultraviolet rays, electron beams, X-rays, α-rays, β-rays, γ-rays, etc. in order from the longest wavelength. Can do. Among these, ultraviolet rays are the most preferable radiation from the viewpoint of economy and efficiency. As the ultraviolet ray used in the present invention, ultraviolet light oscillated from a lamp such as a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, an arc lamp or a xenon lamp can be preferably used. The radiation having a shorter wavelength than ultraviolet rays has high chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy (Reference JP 2003-176344).

  In addition, the above-mentioned various thermosetting resins, thermoplastic resins, radiation curable resins and the like mixed as polymer alloys, those resins bonded by chemical bonds, block polymers of these resins, Also included are graft polymers.

  Further, in the present invention, the polymer precursor before polymerization of the resin, or an organic resin matrix precursor that becomes the resin after molding by heating, photopolymerization, or other chemical reaction in a monomer state, and a compound such as a compound are also included in the resin. Included in the matrix.

  Further, the relative dielectric constant of the resin matrix is preferably less than 10 at 1 GHz, particularly preferably less than 5, more preferably less than 4, and still more preferably less than 3.5. When the relative dielectric constant is 10 or more, characteristics such as dielectric loss tangent are sacrificed by increasing the dielectric constant of the resin matrix, so that the loss is large on the high frequency side, which is not preferable as a high frequency electronic material. The value of dielectric loss tangent of the resin matrix is preferably less than 0.5, more preferably less than 0.4, and still more preferably less than 0.3. When the value of the dielectric loss tangent is 0.5 or more, the loss at the original high frequency is large, which is not preferable as an electronic material for high frequency.

  The lowest temperature among the melting point, softening point, or glass transition point of the resin matrix is preferably 60 ° C to 500 ° C, more preferably 80 ° C to 450 ° C, and 100 ° C to 400 ° C. More preferably. This is because solder heat resistance is insufficient when the temperature is lower than 60 ° C., and when the temperature is 500 ° C. or higher, it is difficult to keep the shape of the nanotube or nanowire in a nano state or a dispersed state.

  The linear expansion coefficient at the lowest or lower temperature among the melting point, softening point or glass transition point of the organic resin matrix is preferably 1 ppm or more and less than 1000 ppm, particularly 1 to 300 ppm. In the present specification, the linear expansion coefficient is a value measured according to ASTM D696. The physical property values of each of these organic resin matrices are detailed in the Plastic Data Book (Industry Research Committee 1999).

3. Composite molded body for high-frequency electronic component The resin molded body of the present invention contains the nanotube and / or nanowire in the matrix.

  In particular, as described above, in the resin molded body of the present invention, at least one selected from the group consisting of nanotubes and nanowires in the matrix is a ratio of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix. It is a composite molded body for high-frequency electronic components, characterized in that

  The blending amount of at least one selected from the group consisting of nanotubes and nanowires is preferably 0.001 to 0.01 parts by weight with respect to 100 parts by weight of the matrix.

  It is sufficient that at least one selected from the group consisting of nanotubes and nanowires is dispersed in the matrix.

  However, according to the research of the present inventors, it is preferable that at least one selected from the group consisting of nanotubes and nanowires is dispersed in the organic resin matrix. Accordingly, the present invention includes an organic resin matrix and at least one selected from the group consisting of a plurality of nanotubes and nanowires present in an arrayed state in the organic resin matrix, from the group consisting of the nanotubes and nanowires Provided is a composite molded body for a high-frequency electronic component, wherein at least one selected is present in an amount of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of a matrix when measured by laser microscope observation Is.

  Here, the arrangement state is not particularly limited and includes various arrangement states. For example, the nanotube and the nanowire are partially linked, or the nanotube and the nanowire are partially connected to each other (that is, the nanotube or the nanowire). (A part of the nanowires are connected to each other), and the nanotubes and nanowires are not macroscopically networked, but are isolated in an aggregated state, or a coiled or arcuate shape having a curvature in the range of 0.5 to 5.0 μm Mention may be made of an array of states.

  Examples of the means for measuring the arrangement state include a method of observing with a laser microscope, a scanning electron microscope, and a transmission electron microscope.

  In addition, when observing with the said laser microscope, the quantity which measured the nanotube or nanowire in the observed part (volume) is calculated | required, and volume% is calculated. The amount (volume%) thus measured can be converted to an amount by weight%. The conversion method is as follows.

W1 = (ρ1 × V1) × 100 / ((ρ1 × V1) + (ρ2 × V2))
W2 = 100-W1
Here, in the above formula, ρ1, V1, and W1 indicate the density, volume%, and weight% of the nanotube or nanowire, respectively, and ρ2, V2, and W2 indicate the density, volume%, and weight% of the matrix, respectively. .

  In addition, when the molded object in which the nanotube is dispersed is observed with a laser microscope, the carbon nanotube is detected based on the following principle (see FIG. 5). That is, the position information obtained by focusing the laser beam is taken in based on the difference in refractive index between the resin and the carbon nanotube, and a composite photograph of the image data obtained with the measured thickness Δt is obtained. Since the focused point is a white point, volume% can be obtained by image processing. The measured volume is measured area × measured thickness.

  Furthermore, in the present invention, it is preferable that nanotubes or nanowires having a radius of curvature in the range of 0.5 to 5.0 μm or an aggregate thereof are arranged as described above. More specifically, each (one by one) nanotube or nanowire has the above-mentioned radius of curvature (in short, the nanotube or nanowire itself is bent), or a plurality of nanotubes or nanowires are assembled. It is preferable that the assembly which has the said curvature radius. Here, the radius of curvature is a value measured using a laser microscope.

  The aggregate is a collection of a plurality of nanotubes or nanowires, particularly about 2 to 100, has a diameter of about 1 to 100 nm, particularly about 2 to 70 nm, and a length of about 0.1 to 20 μm, especially 0. It is a string-like, coil-like, or arc-shaped aggregate of about 2 to 10 μm.

  Among these, in the organic resin matrix, those in which the average adjacent distance between the nanotubes, nanowires, or aggregates thereof is 0.1 to 10 μm, particularly 0.1 to 7 μm are preferable.

  Here, the average adjacent distance is a value obtained by observing a nanotube or nanowire dispersed in an organic matrix or an aggregate thereof with a laser microscope. Specifically, in a photograph of the molded body of the present invention taken with a laser microscope, the volume occupied by one is determined from the value obtained by dividing the volume of the observation field by the number of nanotubes or nanowires or their aggregates, The cube root of the volume occupied by one was taken as the average adjacent distance.

  Moreover, the average adjacent distance of a nanotube or nanowire or an aggregate thereof is obtained as follows. The average adjacent distance is determined from the number of nanotubes or nanowires or their aggregates observed by laser microscope observation and the observed volume. It is a preferable form that the nanotube or nanowire is connected to each other in a range of 0.1 to 10 μm (that is, the nanotube or nanowire is connected to each other).

  Further, it is preferable that nanotubes or nanowires are partially aggregated and arranged in the direction in which an electric field or a magnetic field is applied in the organic resin matrix.

  In particular, the transition metal-containing nanoscale carbon tube, particularly the iron-carbon composite (ie, (a) a carbon tube selected from the group consisting of nanoflake carbon tubes and nested multi-walled carbon nanotubes; and (b) iron carbide or iron. And (b) an iron carbide-carbon composite filled with iron carbide or iron in the range of 10 to 90% of the space in the tube of the carbon tube (a)), a matrix, In particular, it is preferably contained in an amount of about 0.0001 to 0.1 parts by weight, particularly 0.001 to 0.01 parts by weight, per 100 parts by weight of the matrix made of an organic resin.

4). Manufacturing method of composite molded body for high-frequency electronic parts and resin composition used in the manufacturing method In order to manufacture the composite molded body for high-frequency electronic parts of the present invention, at least selected from the group consisting of nanotubes and nanowires according to a conventional method One type may be dispersed in a matrix material such as the low-molecular organic matrix, organic resin matrix, low-molecular inorganic matrix, inorganic resin matrix, and composites thereof. As this dispersion method, for example, a dispersion method used for carbon compounds such as ordinary carbon black, and a method used for dispersing an inorganic filler or the like can be employed without particular limitation.

  For example, a method of treating the surface of a nanotube or nanowire with plasma, corona, electron beam, etc., modifying the surface with a coupling material, or adsorbing a surfactant or the like is known. .

  In one preferred embodiment of the present invention, the molded article of the present invention is obtained by blending nanotubes or nanowires with an organic resin in a solution state, a fluid state, or a molten state above the glass transition point or above the melting point, and then a solvent. It is manufactured by solidifying and molding an organic resin by a method of removal, photocuring reaction, thermosetting reaction, or cooling treatment.

  When the matrix is a low-molecular organic matrix, an organic resin matrix, a low-molecular inorganic matrix, an inorganic resin matrix, and a composite thereof, preferable production methods include, for example, the following (A pretreatment step, (B) master Examples of the method include a batch material manufacturing process, (C) a molding material manufacturing process process, and (D) a molding process.

(A) Pretreatment step At least one selected from the group consisting of nanotubes and nanowires is mixed with a resin and a suitable organic solvent, and mixed, for example, with a planetary mill. Moreover, the process for normal carbon dispersion | distribution, for example, the process of applying a plasma, oxidizing the surface, processing with a coupling agent etc., attaching a surfactant etc., can also be adopted.

  The resin used in the pretreatment step may be an organic resin used as the organic resin matrix or a different organic resin.

  In this pretreatment step, it is generally preferable to use an organic solvent. Examples of such organic solvents include acetone, toluene, tetrahydrofuran (THF), methyl ethyl ketone, n-methylpyrrolidone (NMP), cyclohexane, hexane, and the like. The amount of the organic solvent used can be appropriately selected from a wide range, but is generally about 10 to 100% by weight based on the nanotube or nanowire.

(B) Masterbatch material preparation step Nanotubes or nanowires pretreated in the pretreatment step (A) and the material constituting the matrix (ie, the organic resin, etc.) are combined with an appropriate dispersing device such as ceramic. By subjecting it to a dispersion treatment of three rolls, nanotubes or nanowires are uniformly dispersed in a matrix material (resin or the like) to prepare a master batch material. The concentration of the masterbatch can be appropriately selected from a wide range. Generally, the nanotube or nanowire is 0.01 to 50 parts by weight, particularly 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin. Part by weight, in particular 0.05 to 10 parts by weight, is preferred.

(C) Molding material preparation step In this step, the master batch obtained in the master batch treatment step and the matrix material (such as the resin) are diluted uniformly according to the composition. As this dilution method, various methods can be adopted. For example, a master batch is prepared from a matrix material (resin by a mixing / dispersing / defoaming apparatus (for example, trade name “Awatori Nertaro”, manufactured by Shinky Corporation). Etc.) can be exemplified by a method of diluting and mixing. Preferably, in this step, an array structure in which the base polymer and the master batch material are partially agglomerated by shear stress is formed in the molding material.

  More specifically, the nanotube or nanowire is 0.01 to 50 parts by weight, particularly 0.01 to 10 parts by weight, preferably 100 to 10 parts by weight of the nanotube or nanowire in the organic resin matrix. Mix and disperse in advance at a concentration of 0.05 to 10 parts by weight, and use the concentrated mixed dispersion to disperse carbon nanotubes or nanowires to 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the organic resin matrix. Thus, a resin composition for a composite molded body for a high-frequency electronic component is manufactured.

  Therefore, the present invention provides the resin composition described in the above step (C), that is, at least one selected from the group consisting of nanotubes and nanowires in the matrix (particularly, organic resin matrix), 100 parts by weight of the matrix. The present invention provides a composition for a composite molded body for a high-frequency electronic component, which is contained in an amount of 0.0001 to 0.1 part by weight based on the above.

(D) Molding step In this molding step (D), the resin composition obtained in the step (C) is molded. Various methods can be employed as the molding method. For example, the molding is performed by solvent removal, photocuring reaction, thermosetting reaction, cooling treatment, coating, heat treatment or the like.

  Preferably, in order to positively impart directionality to the array structure of nanotubes or nanowires, a shearing force may be applied in a desired direction, and the transition metal-containing nanoscale carbon tube, particularly iron An electric field or a magnetic field may be applied to a resin composition using a nanoscale carbon tube containing

  When the above resin composition is molded under the application of an electric field or a magnetic field, some of the nanotubes or nanowires are connected to each other and solidified in a coiled or arcuate state having a curvature range of 0.5 to 5.0 μm. Can be molded. Therefore, according to one embodiment of the present invention, under application of an electric or magnetic field, a part of the nanotubes or nanowires are connected to each other and in a coiled or arcuate state having a curvature range of 0.5 to 5.0 μm, There is provided a method for producing a composite molded body for a high-frequency electronic component, characterized by solidifying and molding.

  In addition, as one embodiment of the molding method of the present invention, a resin composition containing 0.0001 to 0.1 parts by weight of carbon nanotubes or nanowires with respect to 100 parts by weight of the organic resin matrix obtained in the step (C) is usually used. According to the method, a resin varnish is formed and a layer is formed on the film, or a method of applying the resin varnish to a substrate as it is and molding can also be adopted.

  The resin varnish and the molding method (molded body production method) using the varnish will be described as follows.

  A solvent may be used when applying and impregnating the nanotube composite molded body or nanowire composite molded body for a printed wiring board according to the present invention on a substrate. These solvents include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylacetamide, methanol, ethanol, etc., and these may be used in combination. Good.

  The nanotube composite molded article or nanowire composite molded article varnish for printed wiring board obtained by blending the components (a) to (e) as described in the section of “2. Matrix” is a glass cloth, a glass nonwoven fabric or a paper. By impregnating a base material such as a cloth containing components other than glass and drying in a drying oven in the range of 80 to 200 ° C., a prepreg of a nanotube composite molded body for a printed wiring board or a nanowire composite molded body is obtained.

The prepreg is used, for example, for producing a printed wiring board or a metal-clad laminate by heating and pressing in the range of 150 to 250 ° C., 20 to 80 kgf / cm ² and 0.1 to 3 hours.

  Drying here means removing the solvent when a solvent is used, and eliminating fluidity at room temperature when no solvent is used.

  Furthermore, according to the present invention, an insulating film can also be produced by casting or braiding the organic resin matrix containing the predetermined amount of nanotubes or nanowires, or the varnish.

  Therefore, the present invention also provides an insulating film manufacturing method characterized by casting or braiding an organic resin matrix containing nanotubes or nanowires, and an insulating film obtained by the manufacturing method.

5. Electronic Parts Since the molded article of the present invention has a low dielectric loss tangent, it can be suitably used as a circuit board material for electrical and electronic equipment, particularly a circuit board material for the GHz band. More specifically, the molded body of the present invention is suitable for manufacturing electronic parts such as printed wiring boards, resin insulating films, resin-coated metal foils, solder resists or semiconductor sealing resins, and interposers.

  Further, as described above, the resin composition of the present invention obtained in the above step (c) contains nanotubes or nanowires in an organic resin matrix, and is useful as a resin adhesive for electronic parts, solder resist ink, etc. It is.

  Accordingly, the present invention also provides a resin adhesive for electronic parts comprising at least one selected from the group consisting of nanotubes and nanowires in a matrix, particularly an organic resin matrix.

  The resin composition (or adhesive) for electronic parts, containing the predetermined amount of nanotubes or nanowires in the organic resin matrix, is also useful for the production of resin insulation films, resin-coated metal foils, solder resists or semiconductor encapsulating resins, etc. It is. Methods for producing these resin insulation films, metal foils with resin, solder resists or semiconductor encapsulating resins using the resin composition (or adhesive) of the present invention are well known to those skilled in the art. Any method known in the art can be used. For example, as described above, the resin composition (or adhesive) comprising the organic resin matrix containing the predetermined amount of the nanotube or nanowire of the present invention is cast or bladed, or screen printing, various roll coaters or the like are used. Thus, an insulating film can be manufactured.

  Accordingly, the present invention provides a resin insulating film, a resin-coated metal foil, a solder resist, or a semiconductor formed by using a resin composition (or adhesive) for electronic components containing the predetermined amount of nanotubes or nanowires in an organic resin matrix. It also provides a sealing resin.

  Further, the resin insulating film, the metal foil with resin, the solder resist, the semiconductor sealing resin and the like are applied to the production of an electric circuit or a printed wiring board according to a conventional method. Therefore, the present invention provides a resin insulating film, a resin-coated metal foil, a solder resist, and a semiconductor encapsulating resin formed using a resin composition (or adhesive) for electronic components containing nanotubes or nanowires in an organic resin matrix. It also provides the used electronic components and printed wiring boards.

  Moreover, when the composition (or adhesive) of the present invention is used, an electric circuit or a printed wiring board can be easily produced. For example, an adhesive comprising the resin composition of the present invention is used as a varnish according to a conventional method, and a metal foil is laminated on one or both sides of at least one prepreg obtained by impregnating and drying the substrate, and heated. A printed wiring board or electric circuit obtained by pressure molding can be produced.

  Therefore, the present invention uses at least one or more prepregs obtained by impregnating and drying a base material with the composition containing the predetermined amount of the nanotubes or nanowires of the present invention, and a metal foil on one or both sides thereof. The present invention also provides a printed wiring board characterized in that a metal-clad laminate obtained by laminating and forming by heating and pressing is formed, and a circuit is formed in the metal-clad laminate.

  Furthermore, according to one embodiment of the present invention, the varnish comprises a composition containing at least one selected from the group consisting of nanotubes and nanowires in the matrix in an amount of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix. Also provided is a printed wiring board or multilayer substrate obtained by using an insulating film obtained by applying and drying the varnish on a film.

  Furthermore, an electronic component or an electrical device can be obtained using the electrical circuit or printed wiring board obtained above. Accordingly, the present invention also provides an electronic component or an electric device that uses the above-described electric circuit or printed wiring board and the electric circuit as a part of the component.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples, and various modifications can be made.

Experiments 1 and 2
In Experiment 1 (Examples 1 to 6 and Comparative Examples 1 to 3 below) and Experiment 2 (Examples 7 to 9 and Comparative Examples 4 and 5 below), the following organic resin matrix and nanotubes were used.

  That is, as an organic resin matrix, a thermosetting epoxy resin (1) (high-Tg material manufactured by Hitachi Chemical Co., Ltd., bisphenol A diglycidyl ether monomer as a main component), or a thermosetting epoxy resin (2) (Hitachi Chemical Industry) A low dielectric constant material, a bisphenol A diglycidyl ether monomer aromatic ring methyl group-substituted product, and a component containing an aromatic ring structure / COOH group) were used.

  The relative permittivity at 1 GHz of each of thermosetting epoxy resin (1) and thermosetting epoxy resin (2) is 3.33, 2.833, dielectric loss tangent is 0.0450, 0.0069, and glass transition temperature is 60 ° C or higher and lower than 500 ° C. Met.

  As nanotubes (iron-carbon composites), the following iron-carbon composites (1) and (2) were used in the proportions shown in Table 1. Table 1 shows the compounding amount (parts by weight) of the nanoscale carbon tube with respect to 100 parts by weight of the solid content of the thermosetting epoxy resin.

<Nanotube (1)>
This nanotube (1) is an iron-carbon composite produced according to the method described in the aforementioned Japanese Patent No. 3569806, and iron carbide is partially encapsulated in the space in the tube of the nano flake carbon tube, Has the following physical properties:
Outer diameter: 20-100nm
Length: 5μm or less Iron carbide content: 10wt%
A transmission electron microscope (TEM) photograph of this iron-carbon composite (1) is shown in FIG.

<Nanotube (2)>
This nanotube (2) contains iron in a multi-walled carbon nanotube and has the following physical properties:
Outer diameter: 10-50nm
Length: 5μm or less Iron carbide content: 3wt%
A transmission electron microscope (TEM) photograph of the nanotube (2) is shown in FIG.

In addition, the content of Fe contained in the nanotube (1) (iron-carbon composite) and the nanotube (2) (iron-containing multi-walled carbon nanotube) used as the nanotube is a composition analysis by ICP analysis, a TEM observation, and a crystal structure by XRD. As a result of analysis, the amount of weight loss of TG / DTA was 9.1 wt% and 3.7 wt% as iron carbide Fe ₃ C, respectively.

Examples 1-6
<(A) Pretreatment step and (B) Masterbatch material preparation step>
After mixing thermosetting epoxy resin (1), nanotube (1) or (2) (iron-carbon composite) and methyl ethyl ketone (manufactured by Nacalai Tesque Co., Ltd.) with an ultrasonic homogenizer, the mixture is stirred with a wet jet mill. A master batch material (the amount of nanotube added to 100 parts by weight of the resin was 0.25 parts by weight) was obtained by a pretreatment process and a master batch process in which the nanotubes were uniformly dispersed in the resin.

<(C) Molding material production process>
Mixing, dispersing and defoaming equipment (trade name “Awatori Neritaro”, Shinky Co., Ltd.), master batch material and thermosetting epoxy resin (1) obtained by the above treatments (A) and (B) The molding material was obtained by diluting and mixing the master batch material with a photosensitive resin.

<(D) Molding process>
Subsequently, the processed molding material, that is, the thermosetting epoxy resin (1) or the composite material of the thermosetting epoxy resin (2) and the iron-carbon composite is vacuum-desolved in vacuum, and the spacer is used. The formed mold was filled with a material and subjected to hot press molding to obtain a plate-like molded body having a thickness of 2 mm, a width of 150 mm, and a length of 50 mm. Further, the molded body was cut to produce a dielectric property evaluation sample of 2 mm × 2 mm × 150 mm.

  When the samples for evaluation of Examples 1 to 5 obtained in this way were observed with a laser microscope, the above-mentioned nanotubes used resulted in a curve in which they were agglomerated in a partially connected state (that is, a part of the nanotubes connected to each other). The part had an array structure with a radius of curvature of 1 to 10 μm.

Comparative Examples 1-3
Evaluation for comparison in the same manner as in Examples 1 to 5 except that the amount of the iron-carbon composite used is the amount shown in Table 1 with respect to 100 parts by weight of the solid content of the thermosetting epoxy resin. A sample was obtained.

  When the comparative evaluation sample thus obtained was observed with a laser microscope, nothing was observed in Comparative Example 1 because no nanotube was added. In Comparative Examples 2 and 3, since the amount of nanotubes added was excessive, the used nanotubes were aggregated in a continuous connection state.

Test example 1
With respect to the samples obtained in Examples 1 to 5 and Comparative Examples 1 to 4, the dielectric loss tangent (tan δ) was measured according to the cavity resonator method (test method for microwave dielectric properties of JIS R1641 fine ceramics substrate). Table 1 shows the measurement results at 5 GHz.

  In Table 1, “change amount%” is a value obtained by dividing the change amount of the dielectric loss tangent of the evaluation sample by the reference value with the dielectric loss tangent of the organic resin matrix not added with the nanotube as a reference value. If the dielectric loss tangent decreases, the amount of change becomes negative, indicating that the effect of reducing the dielectric loss tangent of the organic resin matrix can be obtained in the GHz band. On the other hand, if the dielectric loss tangent increases, the amount of change becomes positive, indicating that there is no effect.

  Table 1 shows the evaluation results of the dielectric loss tangent tan δ of the molded body produced from the combination of the resin (1) and the nanotube (1). Compared to Comparative Example 1 in which no nanotube is added, Examples 1 to 3 within the scope of the present invention show a decrease in dielectric loss tangent. In Comparative Example 2, the dielectric loss tangent increased significantly when nanotubes were added beyond the scope of the invention.

  Note that “change amount%” indicates the percentage of increase / decrease relative to tan δ = 0.0453 in Comparative Example 1 at 5.0 GHz.

Examples 7-9
A sample for evaluation was prepared in the same manner as in Examples 1 to 6 except that the thermosetting epoxy resin (2) was used and the amount of the iron-carbon composite (nanotube (1)) was changed to the amount shown in Table 2. Obtained.

  When the samples for evaluation of Examples 7 to 9 obtained in this way were observed with a laser microscope, the above-mentioned nanotubes were used to be agglomerated in a connected state by a part (that is, a part of the nanotubes connected to each other). The part had an array structure with a radius of curvature of 1 to 10 μm.

Comparative Examples 4 and 5
A sample for evaluation was prepared in the same manner as in Examples 1 and 2 except that the thermosetting epoxy resin (2) was used and the amount of the iron-carbon composite (nanotube (1)) was changed to the amount shown in Table 2. Obtained.

  In Comparative Example 4 thus obtained, nothing was observed because no nanotubes were added. In Comparative Example 5, the added amount of the nanotubes was excessive, so that the used nanotubes were aggregated in a continuous connection state.

Test example 2
With respect to the samples for evaluation obtained in Examples 7 to 9 and Comparative Examples 4 and 5, the dielectric loss tangent was measured in the same manner as in Test Example 1. The results are shown in Table 2. In Table 2, “change amount%” indicates the percentage of increase / decrease relative to tan δ = 0.0074 in Comparative Example 4 at 5.0 GHz.

  Table 2 shows the evaluation results of the dielectric loss tangent tan δ of the molded body produced from the combination of the resin (2) and the nanotube (1). Compared to Comparative Example 4 in which no nanotube was added, Examples 7 to 9 within the scope of the present invention show a decrease in dielectric loss tangent.

Experiment 3
Examples 10-17
As an organic resin matrix, epoxy acrylate resin (EAM-2160 manufactured by Nippon Kayaku Co., Ltd.), photopolymerization initiator (DETX-S manufactured by Nippon Kayaku Co., Ltd.) 2 wt%, photopolymerization accelerator (EPA manufactured by Nippon Kayaku Co., Ltd.) 2 wt% A photosensitive resin mixed with% was used.

  The epoxy acrylate resin used had a relative dielectric constant at 1 GHz of 3.33, a dielectric loss tangent of 0.037, and a glass transition temperature of 60 ° C. or higher and lower than 500 ° C.

  As the transition metal-containing nanoscale carbon tube, the nanotube (1) and the nanotube (2) used in Examples 1 to 9 were used.

<(A) Pretreatment process>
After mixing the above resin, nanotube (1) or (2), acetone (manufactured by Nacalai Tesque Co., Ltd.) and zirconia oxide ball (manufactured by Toray) at 400 rpm with a planetary mill (manufactured by Fletsch Japan), the zirconia ball is removed. Then, acetone was removed by drying to obtain a pretreated transition metal-containing nanoscale carbon tube.

<(B) Masterbatch material production process>
The pretreated nanotube (1) and nanotube (2) and photosensitive resin are mixed with a ceramic three roll (manufactured by Noritake Company, NR-42A), and the nanotubes are uniformly dispersed in the resin to obtain a master batch material. (The amount of carbon nanotubes added to 100 parts by weight of the resin was 0.1 parts by weight of the nanotube (1) and 0.26 parts by weight of the nanotube (2)).

<(C) Molding material production process>
According to the composition shown in Table 5 below, the processed masterbatch material and the photosensitive resin are mixed in Tables 3 and 4 using a mixing / dispersing / defoaming apparatus (trade name “Awatori Nertaro”, manufactured by Shinky Co., Ltd.). As shown, a molding material was obtained by diluting and mixing the masterbatch material with a photosensitive resin.

<(D) Molding process>
The molding material obtained above was put into a cylindrical mold and irradiated with ultraviolet rays (irradiation dose: 6 J / cm ² ) with a mercury lamp (500 W) to obtain a cylindrical molded body. An evaluation sample was obtained by hollowing out the central portion of the molded body. The sample for evaluation is a coaxial workpiece, has a donut shape, has an outer diameter of 7 mm, an inner diameter of 3.1 mm, and a height (thickness) of 1 to 3 mm.

  The samples for evaluation of Examples 10 to 17 thus obtained were observed with a laser microscope. As a result, the bent aggregates in a connected state by a part (that is, a part of the nanotubes were connected to each other) by the nanotubes used. The part had an array structure with a radius of curvature of 1 to 10 μm.

Comparative Examples 6-8
Samples for evaluation for comparison were obtained in the same manner as in Examples 10 to 17 except that the amounts of the nanotubes (1) and (2) used were the amounts shown in Table 5.

  When the evaluation samples of Comparative Examples 6 to 8 thus obtained were observed with a laser microscope, nothing was observed in Comparative Example 6 because no carbon nanotubes were added. In Comparative Examples 7 and 8, since the amount of carbon nanotubes added was excessive, the used nanotubes had a structure in which they were aggregated in a continuous connection state.

Test Example 3: Measurement of dielectric loss tangent by coaxial method The dielectric loss tangent of the evaluation samples obtained in Examples 10 to 17 and Comparative Examples 6 to 8 was measured by the coaxial method.

  Evaluation of the complex dielectric constant in the GHz band by the coaxial method was carried out by measuring tan δ and relative dielectric constant in the GHz band according to the method described in Satoru Kurokawa et al., Kyoto Prefectural Small Business Center Technical Report, 2002, No. 30.

That is, the measurement was performed by a method for obtaining a complex dielectric constant by inserting a measured material processed into a coaxial shape of a coaxial connector of APC7mm standard with a vector network analyzer and measuring two S parameters of S11 and S21. .
Sample shape: inner diameter 3.1 mm, outer diameter 7 mm, thickness 1-3 mm

  In Table 5, “Change%” indicates the percentage of increase / decrease relative to tan δ of Comparative Example 6 at 5.1 GHz.

  Comparative Example 7 and Examples 10 to 13 in Table 5 are evaluation results of the dielectric loss tangent tan δ of the molded body produced by combining the photosensitive resin and the nanotube (1). Compared to Comparative Example 6 in which no nanotube was added, Examples 10-13 within the scope of the present invention show a decrease in dielectric loss tangent.

  In addition, Comparative Example 8 and Examples 14 to 17 in Table 5 are evaluation results of dielectric loss tangent tan δ of a molded body made of a combination of the photosensitive resin and the nanotube (2). Compared to Comparative Example 6 in which no nanotube was added, Examples 14 to 17 within the scope of the present invention show a decrease in dielectric loss tangent.

Experiment 4
The result of having evaluated the sample produced using the same molding material as experiment 3 and changing only a molding process is shown.

Examples 18-22
As resin, epoxy acrylate resin (EAM-2160 manufactured by Nippon Kayaku Co., Ltd.), photopolymerization initiator (DETX-S manufactured by Nippon Kayaku Co., Ltd.) 2 wt%, photopolymerization accelerator (EPA manufactured by Nippon Kayaku Co., Ltd.) 2 wt% A mixed photosensitive resin was used.

  As the nanotube (transition metal-containing nanoscale carbon tube), the nanotube (1) and the nanotube (2) used in Examples 1 to 12 were used.

  The molding material produced in Example 10, 12, 13, 14 or 16 was used as shown in Table 6. The pretreatment step (A), masterbatch material preparation step (B), and molding material preparation step (C) are the same as in Example 10, 12, 13, 14 or 16, but the molding step (D) is as follows. I went to.

<(D) Molding process>
The obtained molding material was applied with a thickness of about 200 μm in the blade method so that shearing was applied in the molding direction of the blade. Ultraviolet rays (irradiation dose: 6 J / cm ² ) were irradiated with a mercury lamp (500 W), and further coated with a thickness of about 200 μm, and ultraviolet irradiation was repeated with a mercury lamp to obtain a molded body having a thickness of about 2.5 mm.

  When the samples for evaluation of Examples 18 to 22 obtained in this way were observed with a laser microscope, the above-mentioned nanotubes were used to be agglomerated in a connected state (partially connected to each other). The part had an array structure with a radius of curvature of 1 to 10 μm.

  The arrangement structure state on the film surface was compared with Example 14 produced by the blade coating method, compared with Example 14 produced by the casting method. The dispersion state of the nanotubes observed with a thickness of 1.0 μm from the surface was observed with a laser microscope. The distribution in the height direction in which nanotubes having a length of 3 μm were observed was determined. In Example 21, a thickness of 0.1 to 0.3 μm was observed, but in Example 14, a thickness of 0.2 to 0.5 μm was observed. In the former, it was found that the nanotubes were parallel to the film surface. An image diagram showing the difference between the molded body of Example 14 and the molded body of Example 21 is shown in FIG.

Comparative Example 9
The amount of iron-carbon composite used was compared in the same manner as in Examples 18-22 except that the amount of carbon nanotubes added was 0% by weight with respect to 100 parts by weight of the solid content of the photosensitive resin. An evaluation sample for was obtained.

Test Example 4 : Measurement of dielectric loss tangent by coaxial method A sample for evaluation was obtained by hollowing out the central portion of the molded body obtained in Examples 18 to 22 and Comparative Example 9. The sample for evaluation is a coaxial workpiece, has a donut shape, has an outer diameter of 7 mm, an inner diameter of 3.1 mm, and a height (thickness) of 1 to 3 mm. The dielectric loss tangent was measured according to the coaxial method described in Test Example 3. The results are shown in Table 6.

  In Table 6, “Change%” indicates the percentage of increase / decrease relative to tan δ of Comparative Example 9 at 5.1 GHz.

  Examples 18 to 20 in Table 6 are evaluation results of the dielectric loss tangent tan δ of the laminated molded body produced by combining the photosensitive resin and the nanotube (1). Compared to Comparative Example 9 in which no nanotube was added, Examples 21 to 23 within the scope of the present invention show a decrease in dielectric loss tangent.

  In addition, Examples 21 and 22 in Table 6 are evaluation results of the dielectric loss tangent tan δ of the laminated molded body produced by combining the photosensitive resin and the nanotube (2). Compared to Comparative Example 9 in which no nanotube was added, Examples 21 to 23 within the scope of the present invention show a decrease in dielectric loss tangent.

Experiment 5
Examples 23-28
Molding materials were produced in the same manner as in Examples 12, 13, and 10 (see Table 5).

  In Examples 26 to 28, a molding material was newly produced. That is, the composition shown in Table 7 is obtained by mixing a masterbatch material added with 0.1 wt% nanotubes and a photosensitive resin with a mixing / dispersing / defoaming device (trade name “Awatori Nertaro”, manufactured by Shinky Corporation). Thus, the molding material was obtained by diluting and mixing the masterbatch material with the photosensitive resin.

The obtained molding material was put into a cylindrical mold and irradiated with ultraviolet rays (irradiation dose: 6 J / cm ² ) with a mercury lamp (500 W) to obtain a cylindrical molded body. An evaluation sample having a smooth upper surface and lower surface (Ra: 1 μm) was obtained. This sample for evaluation has a disk shape, and the outer diameter is 10 mm and the height is 2 mm.

  When the samples for evaluation of Examples 23 to 28 obtained in this way were observed with a laser microscope, the above-mentioned nanotubes used resulted in a curve in which they were agglomerated in a partially connected state (that is, a part of the nanotubes connected to each other). The part had an array structure with a radius of curvature of 1 to 10 μm.

Comparative Example 10
It produced similarly to the comparative example 6. However, the upper and lower surfaces of the cylindrical molded body were smoothed (Ra: 1 μm).

Test Example 5 : Measurement of dielectric loss tangent by open-type evanescent wave coaxial resonator method Measurement of dielectric loss tangent was performed by the open-type evanescent wave coaxial resonator method. This open-type evanescent wave coaxial resonator method is described, for example, in the document Data-Analysis in the Evanescent Perturbation Method using an Open-ended Coaxial Resonator Probe, Odate et al, Micro wave theory and technic, IEEE, 2005, An evaluation sample (a disc with a thickness of 1 mm or more, a diameter of 10 mm or more, and a single-sided Ra of 1 μm or less) is installed at the tip of the coaxial resonator probe, and a resonance electromagnetic field (evanescent wave) leaking from the tip infiltrates the evaluation sample. As a result, the resonance characteristics (resonance frequency, Q value) of the entire resonator change due to the complex dielectric constant of the evaluation sample. By measuring this change, the dielectric constant and tan δ were calculated.

  Table 7 shows the evaluation results of the dielectric loss tangent tan δ of the molded body produced by combining the photosensitive resin and the carbon nanotube (1). Compared to Comparative Example 10 in which no carbon nanotube was added, Examples 23 to 28 within the scope of the present invention show a decrease in dielectric loss tangent.

  “Change amount%” is the percentage of increase / decrease relative to tan δ of Comparative Example 10 at 5.68 GHz.

Experiment 6
The effect of low dielectric loss tangent was investigated using the same carbonaceous particulate carbon nanoparticles instead of the tubular nanotubes.

Comparative Examples 11-14
As an organic resin matrix, epoxy acrylate resin (EAM-2160 manufactured by Nippon Kayaku Co., Ltd.), photopolymerization initiator (DETX-S manufactured by Nippon Kayaku Co., Ltd.) 2 wt%, photopolymerization accelerator (EPA manufactured by Nippon Kayaku Co., Ltd.) 2 wt% A photosensitive resin mixed with% was used.

  Further, instead of nanotubes, highly conductive carbon black (Ketjen Black) was used in the proportions shown in Table 8. Table 8 shows the amount (parts by weight) of ketjen black based on 100 parts by weight of the photosensitive resin.

<(A) Pretreatment process>
Resin, Ketjen Black (manufactured by Ketjen Black International Co., Ltd.), PEGME (polyethylene glycol methyl ether), Acetone (manufactured by Nacalai Tesque Co., Ltd.), and oxidized zirconia balls were mixed with a planetary mill at 400 rpm for 1 hour, and then oxidized zirconia balls And acetone was removed by drying to obtain a pretreated ketjen black.

<(B) Masterbatch material production process>
Ketjen black coated with the above pretreated resin and the resin are mixed by a ceramic three roll (manufactured by Noritake Co., NR-42A), and the ketjen black is uniformly dispersed in the resin. Part of the ketjen black was 0.1 parts by weight).

<(C) Molding material production process>
According to the formulation composition shown in Table 8, the processed masterbatch material and the photosensitive resin were mixed, dispersed, and defoamed (trade name “Awatori Nertaro”, manufactured by Shinky Corporation) to obtain a molding material.

<(D) Molding process>
The molding material obtained in the above step (C) was placed in a cylindrical mold and irradiated with ultraviolet rays (irradiation dose: 6 J / cm ² ) with a mercury lamp (500 W) to obtain a cylindrical molded body. An evaluation sample was obtained by hollowing out the central portion of the molded body. This sample for evaluation is a coaxial workpiece, has a donut shape, has an outer diameter of 0.7 cm, an inner diameter of 0.3 cm, and a height (L) of 2.7 to 2.9 cm.

  When the samples for evaluation of Comparative Examples 11 to 14 obtained in this way were observed with a laser microscope, the ketjen black used was partially connected to each other (that is, a part of nanotubes or nanowires were connected to each other). The arrangement of the curved portions aggregated at 1 to 10 μm in radius of curvature was not achieved. Compared to carbon nanotubes with a high aspect ratio, ketjen black is a particle, so it cannot form a curved assembly.

Test Example 7
For the samples for evaluation obtained in Comparative Examples 11 to 14, the dielectric loss tangent was measured by the coaxial method in the same manner as in Test Example 3. The results are shown in Table 8.

  “Change%” indicates the percentage of increase / decrease relative to tan δ of Comparative Example 11 at 5.1 GHz.

Experiment 7
Impurity analysis of the nanotube (1) and the nanotube (2) was performed. That is, Table 9 shows the results of analysis of chlorine, fluorine and bromine contents by ion chromatography after combustion at 1350 ° C.

Experiment 8
As an Example using a thermosetting resin, the preferable form in the case of mix | blending an iron-carbon composite body with the epoxy resin currently implemented as an insulating material for printed circuit boards is shown.

Example 29
(A) 100 parts by weight of a bisphenol A novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name Epicron N-865, epoxy equivalent 207) as an epoxy resin, (b) bisphenol as an addition condensate of bisphenol A and formaldehyde 24.5 parts by weight of A novolak resin (Dainippon Ink & Chemicals, trade name Phenolite VH-4170, hydroxyl group equivalent 114), (c) 1-cyanoethyl-2-ethyl-4-methyl as a curing accelerator Melamine-modified phenol novolak resin (manufactured by Dainippon Ink & Chemicals, Inc., as a compound having a nitrogen content of 60% by weight or less containing 0.3 parts by weight of imidazole and (d) a compound having a triazine ring or an isocyanuric ring or a urea derivative Name Phenolite LA-7054, 34.2 parts by weight of an elemental content (14% by weight) is dissolved in methyl ethyl ketone, and (e) an nanotube (an iron-carbon composite in which iron carbide is partially included in the inner space of the nanoflake carbon tube) (Product name MetaCarbo, manufactured by Osaka Gas Co., Ltd.) was added in an amount of 0.008 parts by weight to prepare a nanotube composite molded varnish for printed wiring boards having a nonvolatile content of 70% by weight.

Example 30
100 parts by weight of bisphenol A novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name Epicron N-865, epoxy equivalent 207), bisphenol A novolak resin (Dainippon Ink Chemical Co., Ltd., trade name Phenolite VH) -4170, hydroxyl group equivalent 114) 23.2 parts by weight, melamine-modified phenol novolac resin (Dainippon Ink & Chemicals, trade name Phenolite LA-7054, nitrogen content 14% by weight) 13.3 parts by weight and tetra Bromobisphenol A (trade name Fireguard FG-2000, manufactured by Teijin Chemicals Ltd., hydroxyl equivalent 272, bromine content 58% by weight) 47.5 parts by weight, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.3 Dissolve parts by weight with methyl ethyl ketone, and add (e) Tube added (Osaka Gas Co., Ltd., trade name Metakabo) 0.008 parts by weight, to prepare a non-volatile content of 70 wt% of the printed wiring board nanotube composite compact varnish.

Example 31
100 parts by weight of bisphenol A novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd. trade name, Epicron N-865, epoxy equivalent 207), bisphenol A novolak resin (Dainippon Ink Chemical Co., Ltd. trade name, Phenolite VH) -4170, hydroxyl equivalent 114) 5.8 parts by weight, benzoguanamine-modified phenol novolak (manufactured by Dainippon Ink & Chemicals, trade name Phenolite LA-7054V, nitrogen content 7% by weight) 31.3 parts by weight, tetrabromo Bisphenol A (trade name manufactured by Teijin Chemicals Ltd., Fireguard FG-2000, hydroxyl group equivalent 272, bromine content 58% by weight) 47.9 parts by weight, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.3 weight Part is dissolved with methyl ethyl ketone, and (e) car Nanotube added (Osaka Gas Co., Ltd. trade name Metakabo) 0.008 parts by weight, to prepare a non-volatile content of 70 wt% of the printed wiring board nanotube composite compact varnish.

Example 32
Brominated bisphenol A type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESB400T, epoxy equivalent 400, bromine content 49% by weight) 100 parts by weight, bisphenol A novolak resin (manufactured by Dainippon Ink & Chemicals, Inc., product) Name Phenolite VH-4170, hydroxyl group equivalent 114) 20.2 parts by weight, melamine-modified phenol novolak resin (manufactured by Dainippon Ink & Chemicals, trade name Phenolite LA-7054, nitrogen content 14% by weight) 9.3 Part by weight, 0.3 part by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole is dissolved with methyl ethyl ketone, and 0.008 part by weight of (e) nanotube (trade name MetaCarbo, manufactured by Osaka Gas Co., Ltd.) is added thereto. Nanocomposite molded body crocodile for printed wiring board having a nonvolatile content of 70% by weight It was produced.

Example 33
100 parts by weight of bisphenol A novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name Epicron N-865, epoxy equivalent 207), bisphenol A novolak resin (Dainippon Ink Chemical Co., Ltd., trade name Phenolite VH) -4170, hydroxyl equivalent 114) 35.3 parts by weight, tetrabromobisphenol A (manufactured by Teijin Chemicals Ltd., trade name Fireguard FG-2000, hydroxyl equivalent 272, bromine content 58% by weight) 47.3 parts by weight, melamine (Nitrogen content 66.7% by weight) 32.3 parts by weight, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.3 parts by weight were dissolved in methyl ethyl ketone, and (e) nanotube (Osaka Gas Co., Ltd.) was dissolved therein. (Product name: MetaCarbo) 0.008 parts by weight, non-volatile content 70% by weight To produce a nanotube composite molding varnish for printed wiring board.

Comparative Example 15
100 parts by weight of bisphenol A novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name Epicron N-865, epoxy equivalent 207), bisphenol A novolak resin (Dainippon Ink Chemical Co., Ltd., trade name Phenolite VH) -4170, hydroxyl equivalent 114) 35.3 parts by weight, tetrabromobisphenol A (manufactured by Teijin Chemicals, trade name Fireguard FG-2000, hydroxyl equivalent 272, bromine content 58% by weight) 47.3 parts by weight, -0.3 part by weight of cyanoethyl-2-ethyl-4-methylimidazole was dissolved in methyl ethyl ketone to prepare an epoxy resin varnish for printed wiring boards having a nonvolatile content of 70% by weight.

Comparative Example 16
Bisphenol A novolak type epoxy resin (Dainippon Ink Chemical Co., Ltd. trade name, Epicron N-865, epoxy equivalent 207) 100 parts by weight, melamine-modified phenol novolak resin (Dainippon Ink Chemical Co., Ltd. trade name, Phenolite) LA-7054, nitrogen content 14% by weight) 61.4 parts by weight, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.3 parts by weight dissolved in methyl ethyl ketone, for printed wiring board having a nonvolatile content of 70% by weight An epoxy resin varnish was prepared.

Comparative Example 17
100 parts by weight of bisphenol A novolak type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-865, epoxy equivalent 207), melamine modified phenol novolak resin (Dainippon Ink Chemical Co., Ltd., trade name Phenolite) LA-7054, nitrogen content 14% by weight) 38.7 parts by weight, tetrabromobisphenol A (manufactured by Teijin Chemicals Ltd., trade name Fireguard FG-2000, hydroxyl group equivalent 272, bromine content 58% by weight) 48.5 Part by weight, 0.3 part by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole was dissolved with methyl ethyl ketone to prepare an epoxy resin varnish for printed wiring boards having a nonvolatile content of 70% by weight.

Comparative Example 18
Low brominated epoxy resin (Dow Chemical Japan Co., Ltd., trade name DER-518, bromine content 21% by weight, epoxy equivalent 485) 80 parts by weight, o-cresol novolac type epoxy resin (Dainippon Ink Industries, Ltd.) In addition, 20 parts by weight of trade name Epicron N-673, epoxy equivalent 213) was mixed with 1 part by weight of dicyandiamide previously dissolved in ethylene glycol monomethyl ether. As a curing accelerator, 0.2 part by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole is blended and dissolved in ethylene glycol and methyl ethyl ketone to produce an epoxy resin varnish for printed wiring boards having a nonvolatile content of 65% by weight. did.

  Table 10 shows the compositions of the nanotube composite molded body varnish or epoxy resin varnish for printed wiring boards of Examples 29 to 33 and Comparative Examples 15 to 18.

  The nitrogen content in the table indicates the ratio of nitrogen to the resin solid content.

  The abbreviations in Table 10 have the meanings given in Table 11.

  The epoxy resin varnish for printed wiring board obtained in Examples 29 to 33 and Comparative Examples 15 to 18 was impregnated into a glass cloth having a thickness of 0.2 mm, and heated at 160 ° C. for 2 to 5 minutes to obtain a prepreg. . Four obtained prepregs were stacked, 18 μm copper foil was stacked on both sides thereof, and a double-sided copper-clad laminate was produced under a press condition of 175 ° C., 90 minutes, 2.5 MPa.

  The obtained double-sided copper-clad laminate was examined for Tg (glass transition temperature), normal state and copper foil peel strength at 200 ° C., solder heat resistance, water absorption rate, and heat discoloration. These results are shown in Tables 12 and 13.

  The test method was performed as follows.

  Tg: The copper foil was etched and measured by a TMA (thermomechanical analysis) method.

Copper foil peel strength: A line having a width of 10 mm was formed on a laminate by etching, and the strength when peeled at 50 mm / min in the normal direction at 200 ° C. in a vertical direction was measured.
Solder heat resistance: The copper foil was etched, held in a pressure cooker tester for 2 hours, then immersed in 260 ° C. solder for 20 seconds, and the appearance was visually examined.
In the table, ○ indicates that no occurrence of measling or blistering is observed and no abnormality is present, Δ indicates occurrence of measling, and × indicates that blistering has occurred.

  Water absorption: Calculated from the difference in weight before and after the copper foil was etched and held in a pressure cooker tester for 4 hours.

Heat discoloration: The copper foil was etched, treated in the air at 160 ° C. for 5 hours, and then visually evaluated.
A sample having no discoloration was indicated by ◯, a sample having slightly discolored by Δ, and a sample having discolored by ×.

  In Examples 29 to 33 using a compound having a triazine ring or an isocyanuric ring or a compound having a nitrogen content of 60% by weight or less and not containing a urea derivative, the copper foil peel strength is as high as 1.5 kN / m in a normal state, Further, even at 200 ° C., the peel strength of about 50% of the normal state is maintained, and the deterioration at high temperature is small.

  Moreover, since Examples 29-33 uses bisphenol A novolak resin as a curing agent, it has a high Tg of about 140-180 ° C., good solder heat resistance and heat discoloration, and low water absorption.

  On the other hand, Comparative Example 15, which does not contain a compound having a triazine ring or an isocyanuric ring or a nitrogen content not containing a urea derivative and having a content of 60% by weight or less, has a copper foil peel strength at normal temperature and 200 ° C. Low.

  Comparative Example 16 and Comparative Example 17 that do not use bisphenol A novolak as the curing agent are inferior in heat resistance and heat discoloration. Further, Comparative Example 18 using dicyandiamide has a low Tg and a low copper foil peel strength at 200 ° C. Furthermore, the water absorption is large and the solder heat resistance is poor.

  The nanotube composite molded body or nanowire composite molded body for a printed wiring board of the present invention and the printed wiring board using the same are excellent in heat resistance and dielectric properties in a high frequency region, and have good adhesion to a copper foil. Therefore, it is useful as a high Tg printed wiring board excellent in heat resistance that requires higher connection reliability and transmission characteristics than ever, such as a printed wiring board on which an MPU is mounted and a printed wiring board for modules.

Experiment 9
Example 34
In order to evaluate the withstand voltage characteristics of the resin insulation, the evaluation sample was an epoxy acrylate resin (EAM-2160 manufactured by Nippon Kayaku Co., Ltd.) as the transition metal-containing nanoscale carbon tube (nanotube (1)) used in Experiment 3 and the organic resin matrix. ), A photosensitive resin in which 2 wt% of a photopolymerization initiator (DETX-S manufactured by Nippon Kayaku Co., Ltd.) and 2 wt% of a photopolymerization accelerator (EPA manufactured by Nippon Kayaku Co., Ltd.) was used.

  Table 14 shows the compounding amount (parts by weight) of the carbon tube with respect to 100 parts by weight of the photosensitive resin.

  The withstand voltage test of the transition metal-containing nanoscale carbon tube (iron-carbon composite) blended composition was performed by the following withstand voltage measurement method.

Sided copper-clad laminate 12cm square of each sample (FR4, copper thickness 35 [mu] m) each five coated in a thickness of 15 ± 5 [mu] m by an applicator on a copper, is irradiated to cure the ultraviolet at a rate of 1000 mj / cm ² The withstand voltage was measured for each sample, and the minimum value of each was shown in Table 14 as the withstand voltage. The following apparatus was used for the measurement of the thickness and withstand voltage of the resin layer. In Comparative Example 20, heat curing (150 ° C. 60 minutes) was performed after UV curing.

  The test result was about an error due to film thickness variation. Even with the addition of the conductive transition metal-containing nanoscale carbon tube, the withstand voltage of the resin film was not lowered, and the function as a resin insulating film or a solder resist was confirmed.

  In the above measurement, LZ-330C manufactured by Kett Scientific Laboratory was used as the thickness measuring device, and TOS 5101 manufactured by Kikusui Electronics Co., Ltd. was used as the withstand voltage measuring device.

  According to the present invention, it is possible to obtain a resin molded body having a reduced dielectric loss tangent (tan δ) in the GHz band.

  Therefore, by using such a resin molded body, it is possible to provide an electronic component that can be suitably used as a high-frequency electronic component, in particular, a circuit board material for electrical / electronic equipment, particularly a circuit board material for the GHz band.

It is an electron microscope (TEM) photograph of one iron-carbon complex which comprises the carbonaceous material obtained in Example 1 of Unexamined-Japanese-Patent No. 2002-338220. It is an electron microscope (TEM) photograph which shows the presence state of the iron-carbon composite in the carbonaceous material obtained in Example 1 of Unexamined-Japanese-Patent No. 2002-338220. It is the electron microscope (TEM) photograph which made one iron-carbon composite_body | complex obtained in Example 1 of Unexamined-Japanese-Patent No. 2002-338220 into the shape of a ring. In addition, the black triangle ((triangle | delta)) shown in the photograph of FIG. 3 has shown the EDX measurement point for a composition analysis. A schematic diagram of a TEM image of a carbon tube is shown, (a-1) is a schematic diagram of a TEM image of a cylindrical nanoflake carbon tube, and (a-2) is a TEM image of a multi-walled carbon nanotube with a nested structure. It is a schematic diagram. It is a conceptual diagram which shows the principle in the case of observing the molded object in which the nanotube was disperse | distributed with a laser microscope. It is a transmission electron micrograph (TEM) of the nanotube (1) (iron-carbon composite) used in Experiment 1 and 2 grades. It is a transmission electron micrograph (TEM) of the nanotube (2) (iron-containing multi-walled carbon nanotube) used in Experiments 1 and 2. It is an image figure which shows the difference of the molded object of Example 14 and the molded object of Example 21. FIG.

Explanation of symbols

100 TEM image in the longitudinal direction of the nano flake carbon tube 110 Approximate linear graphene sheet image 200 TEM image in a cross section substantially perpendicular to the longitudinal direction of the nano flake carbon tube 210 Arc-shaped graphene sheet image 300 Longitudinal direction of the multi-layered carbon nanotube in a nested structure Straight graphene sheet image continuous over the entire length of 400 TEM image of a cross section perpendicular to the longitudinal direction of a nested multi-walled carbon nanotube

Claims (43)

A composite molded body for a high-frequency electronic component, wherein the matrix contains at least one selected from the group consisting of nanotubes and nanowires in an amount of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix. 2. The composite molded body for a high frequency electronic component according to claim 1, wherein the matrix is selected from the group consisting of a low molecular organic matrix, an organic resin matrix, a low molecular inorganic matrix, an inorganic resin matrix, and a composite thereof. The composite molded body for high-frequency electronic components according to claim 1, wherein the matrix is an organic resin matrix. The organic resin that forms the organic resin matrix
(i) a thermoplastic resin, or
(ii) thermosetting resin, or
(iii) radiation curable resin, or
(iv) a composite resin comprising two or more selected from the group consisting of thermoplastic resins, thermosetting resins and radiation curable resins, or
(v) The composite molded body for a high-frequency electronic component according to claim 3, which is a mixture of two or more of (i) to (iv) above.   5. The composite molded body for a high-frequency electronic component according to claim 1, wherein the matrix has a relative dielectric constant of less than 10 at 1 GHz. 5. The composite molded body for high-frequency electronic components according to claim 1, wherein the matrix has a relative dielectric constant of less than 5 at 1 GHz. The composite molded body for a high-frequency electronic component according to any one of claims 1 to 4, wherein a dielectric loss tangent at 1 GHz of the matrix is less than 0.5.   The matrix is a low molecular organic matrix, an organic resin matrix or a composite thereof, and the lowest temperature among the melting point, softening point or glass transition point of the low molecular organic matrix, the organic resin matrix or the composite thereof is 60. The composite molded body for a high-frequency electronic component according to any one of claims 1 to 7, wherein the composite molded body has a temperature of not lower than 500 ° C and lower than 500 ° C. The matrix is a low-molecular organic matrix, an organic resin matrix, or a composite thereof, and the linear expansion coefficient at the lowest temperature or lower than the melting point, softening point, or glass transition point is 1 ppm or more and less than 1000 ppm. The composite molded body for a high-frequency electronic component according to any one of claims 1 to 7, wherein The composite molded body for a high-frequency electronic component according to any one of claims 1 to 9, wherein at least one selected from the group consisting of the nanotube and the nanowire is formed of a conductive material. The composite molded body for a high-frequency electronic component according to any one of claims 1 to 9, wherein at least one selected from the group consisting of the nanotube and the nanowire is a carbon nanotube. At least one selected from the group consisting of the nanotube and the nanowire is a single-walled carbon nanotube, a multi-walled carbon nanotube, an amorphous nanoscale carbon tube, or a transition metal-containing nanoscale carbon tube, having a diameter of 1 to 100 nm, and 10 to 5000 The composite molded body for high-frequency electronic components according to any one of claims 1 to 9, having an aspect ratio of: At least one selected from the group consisting of the nanotubes and nanowires is a transition metal-containing nanoscale carbon tube, and the transition metal content is 0.1 wt% or more of the weight of the transition metal nanoscale carbon tube in terms of transition metal carbide It is less than 50 wt%, The composite molded object for high frequency electronic components in any one of Claims 1-9 characterized by the above-mentioned. At least one selected from the group consisting of the nanotubes and nanowires is a transition metal-containing nanoscale carbon tube, and the transition metal is at least one selected from the group consisting of iron, cobalt and nickel A composite molded body for a high-frequency electronic component according to any one of claims 1 to 9. At least one selected from the group consisting of the nanotubes and nanowires is a transition metal-containing nanoscale carbon tube, and at least one selected from the group consisting of iron, cobalt, nickel, and their carbides in the inner space of the tube. The amount of at least one selected from the group consisting of iron, cobalt, nickel and their carbides is 1% by weight or more of the weight of the transition metal-containing nanoscale carbon tube in terms of transition metal carbide The composite molded body for high-frequency electronic components according to claim 14. And at least one selected from the group consisting of nanotubes and nanowires and an organic resin matrix, and at least one selected from the group consisting of nanotubes and nanowires is in a partially connected state with respect to 100 parts by weight of the organic resin matrix. A composite molded body for high-frequency electronic components, characterized by being present in a proportion of 0.0001 to 0.1 parts by weight. The composite molded body for a high-frequency electronic component according to claim 16, wherein the nanotube, the nanowire, or an aggregate thereof has a curvature in the range of 0.5 to 5.0 µm. The composite molded body for high-frequency electronic components according to claim 16, wherein free ions contained in the nanotube or nanowire are 200 ppm or less and the halogen content is 400 ppm or less. At least one selected from the group consisting of nanotubes and nanowires is blended with an organic resin in a solution state, a fluid state, or a molten state above the glass transition point or above the melting point, and then solvent removal, photocuring reaction, thermosetting A method for producing a composite molded body for a high-frequency electronic component, characterized in that an organic resin is solidified by reaction or cooling treatment. In an organic resin matrix, at least one selected from the group consisting of nanotubes and nanowires is premixed and dispersed at a concentration of 0.01 parts by weight to 50 parts by weight with respect to 100 parts by weight of the organic resin matrix. A resin composition is produced by dispersing the mixed dispersion in an organic resin matrix so that the carbon nanotubes or nanowires are 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the organic resin matrix. The method for producing a composite molded body for a high-frequency electronic component according to claim 19, wherein the organic resin is solidified by a curing reaction, a thermosetting reaction, or a cooling treatment. 21. The composite molded body for a high-frequency electronic component according to claim 19 or 20, wherein the molded body is solidified and molded in a state where a part of the nanotubes or nanowires are connected to each other in an organic resin matrix under application of an electric field or a magnetic field. Manufacturing method.
A part of nanotubes or nanowires are connected to each other under application of an electric field or a magnetic field, and solidified and molded in a coiled or arcuate state having a curvature range of 0.5 to 5.0 μm. Item 19. A method for producing a composite molded article for a high-frequency electronic component according to Item 19 or 20. The matrix is an organic resin matrix, and the organic resin matrix is (a) an epoxy resin, (b) an addition condensate of bisphenol A and formaldehyde, (c) a curing accelerator, and (d) a compound having a triazine ring or an isocyanuric ring, The composite molded article for a high-frequency electronic component according to claim 1, wherein the compound is a compound excluding a urea derivative and containing a compound having a nitrogen content of 60% by weight or less as an essential component.    (B) The addition condensate of bisphenol A and formaldehyde is in the range of 0.5 to 1.5 equivalents of phenolic hydroxyl group with respect to the epoxy group of the epoxy resin, and (c) the curing accelerator is based on 100 parts by weight of the epoxy resin. Weight of 0.01 to 5 parts by weight and (d) a compound having a triazine ring or isocyanuric ring or a compound containing no urea derivative and having a nitrogen content of 60% by weight or less in a hot air drying furnace at 210 ° C. for 30 minutes The composite molded body for a high-frequency electronic component according to claim 23, wherein the nitrogen content is in a range of 0.1 to 10% by weight with respect to the resin solid content calculated from the ratio.   The composite molded body for high-frequency electronic components according to claim 23 or 24, which contains (e) a flame retardant in addition to (a) to (d).   The composite molded article for a high-frequency electronic component according to claim 25, wherein the retarder of (e) is tetrabromobisphenol A or glycidyl ether of tetrabromobisphenol A. A composition for a composite molded body for a high-frequency electronic component, wherein the matrix contains at least one selected from the group consisting of nanotubes and nanowires in an amount of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix. 28. The composite molded body composition for high-frequency electronic components according to claim 27, wherein the matrix is an organic resin matrix. 29. The composite for high-frequency electronic components according to claim 28, wherein the composition containing nanotubes or nanowires in an organic resin matrix is a resin adhesive for electronic components, a resin insulating film, a solder resist, or a semiconductor sealing resin. Composition for molded article. A composite molded body for a high-frequency electronic component, comprising the composition for a composite molded body for a high-frequency electronic component according to any one of claims 27 to 29. A metal foil with a resin, comprising a cured layer of the composition for a composite molded body for a high-frequency electronic component according to claim 29. A printed wiring board comprising a cured layer of the composition for a composite molded article for a high-frequency electronic component according to claim 29. A method for forming an electric circuit or a method for producing a printed wiring board, comprising using the resin composition for a composite molded article for a high-frequency electronic component according to claim 27. An electronic component using the printed wiring board according to claim 32 as a part of the component. An electric device using the printed wiring board according to claim 32 as a part of a component. An insulating film formed by casting or braiding an organic resin matrix containing at least one selected from the group consisting of nanotubes and nanowires. A method for producing an insulating film, comprising casting or braiding an organic resin matrix containing at least one selected from the group consisting of nanotubes and nanowires. It is obtained by impregnating a substrate with a composition containing at least one selected from the group consisting of nanotubes and nanowires in a matrix of 0.0001 parts by weight to 0.1 parts by weight with respect to 100 parts by weight of the matrix, and drying the substrate. A printed wiring board comprising: a metal-clad laminate obtained by laminating a metal foil on one or both sides of at least one prepreg, and heat-press molding to form a circuit in the metal-clad laminate. In the matrix, a composition containing at least one selected from the group consisting of nanotubes and nanowires in an amount of 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the matrix is used as a varnish, and the varnish is applied onto a film and dried. A printed wiring board or a multilayer substrate obtained by using an insulating film obtained in this way. A resin adhesive for electronic parts comprising at least one selected from the group consisting of nanotubes and nanowires in an organic resin matrix. A resin insulating film, a resin-coated metal foil, a solder resist, or a semiconductor sealing resin formed using the resin adhesive for electronic components according to claim 40. An electric circuit or printed wiring board using a resin insulating film, a resin-coated metal foil, a solder resist, and a semiconductor sealing resin formed using the resin adhesive for electronic parts according to claim 40. The electrical circuit formation method or printed wiring board manufacturing method using the resin adhesive for electronic components of Claim 40.